JP3588513B2 - Variable glitter composition, coated body and coating method - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、光輝性組成物、特にその光輝性が観察角度によって変化する可変光輝性を与える組成物、その塗装体、及びその塗装方法等に関する。
【０００２】
【従来の技術】
塗料や印刷インキにおいて、基材の一部あるいは全部に、その外観を美麗にしたり、高級感を与えるために光輝性を与えることがしばしば要求される。従来より塗装物や印刷物に光輝性を与えるために、アルミニウム粉等の金属粉や雲母チタン系のパール顔料等を塗料やインキ組成物中に分散混合して用いることが一般的であった。
【０００３】
【発明が解決しようとする課題】
しかしながら、例えばこのような金属粉等を用いる方法では、腐食や、比重が高いことによる配向変化のために経時的に光輝感が鈍くなることがあり、また、その光輝性も用いる金属粉の金属色に由来するもので金属粉単独で赤や青と言った有色の光輝性を得ることはできなかった。
一方、雲母チタン系のパール顔料には種々の有色の干渉色を持つものが知られているが、このようなパール顔料においてもの外観色は基本的には白色であり、また、その光輝感もパール様のマットなもので、鮮やかな有色の外観と高い光沢度を望む用途において満足できるものではなかった。
【０００４】
また、光輝性においてはしばしば観察角度による光沢度が著しく異なるフリップフロップ効果が要求されることがあるが、従来の方法では鮮やかな有色の外観色と高い光沢度を発揮し、且つこのフリップフロップ効果も高い塗装体を得ることは困難であった。
本発明はこのような従来技術の課題に鑑み成されたものであり、その目的は、鮮やかな有色の外観色と高い光輝性を発揮し、しかも、フリップフロップ効果の高い可変光輝性の組成物を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは以前に二酸化チタン被覆雲母表面をコバルト、ニッケル、銅より選ばれた１種又は２種以上の金属粒子で被覆することによって得られる顔料が、多彩な有色の外観色と共に光輝性を有することを報告した（特願昭６１−１８８８８７号）。そして、今回この顔料を適正に配合した塗料やインク等の組成物の塗装体が良好な有色の光輝感を発揮するとともに、観察角度による光沢度が著しく変化することを見出した。また、被覆金属として、亜鉛、スズ、金、銀を用いた場合にも、同様の効果が得られることも見出し、本発明を完成するに至った。
【０００６】
すなわち、本発明の請求項１記載の可変光輝性組成物は、二酸化チタン被覆雲母表面がコバルト、ニッケル、銅、亜鉛、スズ、金、銀より選ばれた１種又は２種以上の金属粒子で被覆され、前記金属被覆量が雲母１００重量部に対して１〜６０重量部である光輝性有色顔料と、バインダー樹脂と、有機溶剤を含有し、光輝性有色顔料とバインダー樹脂の配合割合が重量比で１：２〜３．５：１の範囲であることを特徴とする。
【０００７】
本発明の請求項２記載の可変光輝性塗装体は、請求項１記載の可変光輝性組成物が基材上に塗装された塗装体であって、該可変光輝性組成物の乾燥後の塗膜における光輝性有色顔料とバインダー樹脂の重量比が１：２〜３．５：１の範囲にあることを特徴とする。
【０００８】
本発明の請求項３記載の可変光輝性塗装体は、請求項２記載の塗装体において、可変光輝性組成物の乾燥後の塗膜の幾何学的膜厚が０．０１〜０．０７ｍｍの範囲であることを特徴とする。
本発明の請求項４記載の方法は、請求項１記載の可変光輝性組成物を、該可変光輝性組成物の乾燥後の幾何学的層厚が０．０１〜０．０７ｍｍの範囲となるように基材上に塗装することを特徴とする。
【０００９】
【本発明の実施の形態】
以下、本発明の実施の形態について詳述する。
本発明で使用する光輝性有色顔料は基本的に特願昭６１−１８８８８７号に記載されているものであり、その製造方法も特願昭６１−１８８８８７号記載の方法を用いることができる。なお、二酸化チタン被覆雲母表面を被覆する金属種としてコバルト、ニッケル、銅以外に亜鉛、スズ、金、銀を用いた場合にも同様に有色の外観色と光沢度を有する光輝性有色顔料を得ることができることが判明した。従って、本発明で使用する光輝性有色顔料は、雲母表面が二酸化チタンで被覆され、さらに該二酸化チタン被覆雲母表面がコバルト、ニッケル、銅、亜鉛、スズ、金、銀より選ばれた１種又は２種以上の金属粒子で被覆されてなり、且つ該金属被覆量が雲母１００重量部に対して１〜６０重量部であるものである。
【００１０】
この光輝性有色顔料は、雲母、二酸化チタン、金属という基本的に無彩色の無機原料で構成されているにも関わらず、鮮やかな有彩色の外観色を呈し、しかも、その光沢度において優れたものである。また、有機顔料による着色顔料と異なり、その安定性等の顔料特性にも非常に優れている。
本発明の可変光輝性組成物において光輝性有色顔料の配合量は特に限定されないが、組成物全量に対して通常５〜３５重量％が好適である。顔料の配合量が少ないと、隠蔽力が低下し、配合量が過剰になると可変光輝性組成物中で顔料の分散が不均一になったり、組成物塗装体の外観がまだらになったり、組成物の粘度が上昇して作業性や印刷適正等に好ましくない影響を及ぼすことがある。
【００１１】
なお、本発明において可変光輝性組成物とは、基材上の一部、あるいは全部の表面を着色又は賦光沢するのためのものを意味し、例えば塗料又は印刷インキのような組成物である。可変光輝性組成物によって塗装される基材としては、紙、板紙、布、皮革、金属、プラスティック等、可変光輝性を要求する基材であれば特に限定されず、その形状も様々なものが適用可能である。もちろん、予め塗装、印刷、コーティング処理された基材でもよい。
【００１２】
本発明にかかる可変光輝性組成物に配合されるバインダー樹脂とは、光輝性有色顔料を基材上に安定に密着させうる樹脂であり、可変光輝性組成物を基材上に塗装後は該組成物中の溶剤が揮散して光輝性有色顔料を包埋した状態で基材上に被膜を形成するものである。バインダー樹脂は基材との相性や、形成被膜被膜強度、膜厚等によって選択されるので特に限定されないが、通常塗料や印刷インキのバインダーとして用いられているものを使用することができる。例えば、ギルソナイト、マレイン酸樹脂、環化ゴム、硬化ロジン、石油樹脂、ニトロセルロース、アクリル樹脂、ポリウレタン樹脂、塩素化ポリプロピレン、塩化ビニル−酢酸ビニル共重合樹脂、エチレン−酢酸ビニル共重合樹脂、塩化ビニル、ポリエステル樹脂、アルキド樹脂、アマニ油、変性フェノール樹脂、フマル酸樹脂、エポキシエステル樹脂、エポキシアミノ樹脂、エポキシフェノール樹脂、ポリエステル樹脂、ビニル樹脂、ポリアミド樹脂、鉱油ワニス、ケトン樹脂、塩化ゴム、エチルセルロース、尿素樹脂、メラミン樹脂等が挙げられる。
【００１３】
また、本発明に係る可変光輝性組成物に配合される溶剤としては、一般に塗料やインキに用いられる溶剤を用いることが可能であり、通常バインダー樹脂を良好に溶解して作業性を向上させ、且つこの樹脂溶液中に光輝性有色顔料が良好に分散配合できるものであれば特に限定されない。例えば、トルエン、キシレン、ｎ−ヘキサン、シクロヘキサン、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ｎ−プロピル、酢酸ｎ−ブチル、酢酸イソブチル、メタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イゾブチルアルコール、アセトン、メチルエチルケトン、メチルイソブチルケトン、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルアセテート、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルアセテート等が挙げられる。
【００１４】
溶剤としては揮発性の有機溶剤が多く用いられるが、場合によっては水等を配合しても良い。
本発明の可変光輝性組成物においては、本発明の効果を損なわない範囲であれば組成物の特性を調節するために前記必須成分の他に通常塗料やインキに配合されている各種添加剤を配合してもよい。例えば、可塑剤、ワックス、湿潤剤、安定剤、染顔料、静電防止剤、消泡剤、酸化防止剤、レベリング剤、重合禁止剤、フィラー剤等が挙げられる。
【００１５】
本発明において、有色の高い光輝感と、観察方向によって光沢が著しく変化するフリップフロップ効果を得るためには可変光輝性組成物中の光輝性有色顔料とバインダー樹脂の重量比は１：２〜３．５：１であることが好適である。このような可変光輝性組成物を基材上に塗装すると、乾燥により可変光輝性組成物中の溶剤が揮散し、基板上にバインダー樹脂被膜が形成され、光輝性有色顔料はこの被膜中に保持されて、塗膜が形成される。従って、基板上の塗膜中、光輝性有色顔料とバインダー樹脂の重量比は１：２〜３．５：１の範囲に存する。このような組成比を有する塗膜は基板に有色の外観色及び高い光輝感を与え、且つ良好なフリップフロップ効果を発揮する。
【００１６】
また、本発明に係る可変光輝性組成物が基板上に塗装された塗装体において、乾燥後の塗膜の幾何学的膜厚は０．０１〜０．０７ｍｍであることが好適である。
塗膜膜厚が小さい場合には顔料による外観色が希薄で隠蔽力が低く、十分な色調や光沢度、フリップフロップ効果が得られない。一方、塗布膜厚が大きすぎると塗膜がうまくのらずにまだらになることがあり、外観が不均一となりやすく、光沢度やフリップフロップ効果も低下する傾向にある。
【００１７】
本発明における塗装方法は、本発明に係る可変光輝性組成物を基材上の一部又は全部の表面に塗布する方法であり、一般的な印刷方法も含む概念である。本発明の塗装方法としては、従来より行われている塗装方法、印刷方法、コーティング技術を利用することができ、例えば印刷方法としては凸板印刷、凹板印刷、グラビア印刷、スクリーン印刷、フレキソ印刷、オフセット印刷、インキジェット印刷、静電印刷等が利用できる。また、はけ塗り、スプレー塗り、転がし塗り、ステンシル塗り、静電塗り、流し塗り、浸し塗り、ローラー塗り、吹き付け塗り等の塗装方法も用いることができる。
以下に、具体例を挙げて本発明をさらに詳細に説明する。
【００１８】
製造例１ 光輝性有色顔料の製造
Ｉｒｉｏｄｉｎ２０５（金色の干渉色を有するルチル型雲母チタン、***Ｍｅｒｃｋ社製）５０ｇを８×１０−３Ｍ塩化スズ水溶液５００ｍｌに分散させ、濾過後、５×１０−３Ｍ塩化パラジウム水溶液に再度分散させた。濾過後、得られた活性化雲母チタン５０ｇをｐＨ６〜６．５、浴温８０℃に保った次亜リン酸ナトリウム（１０ｇ／ｌ）、クエン酸ナトリウム（１００ｇ／ｌ）、硫酸アンモニウム（５０ｇ／ｌ）、硫酸ニッケル（１１．７５ｇ／ｌ）からなる無電解ニッケルメッキ浴１２００ｍｌに分散させ、１時間撹拌を続けた。濾過後、水洗し、１５０℃で１２時間乾燥させ、金色の外観色を有する光輝性有色顔料５２ｇを得た。
【００１９】
試験例１：顔料と樹脂の比率
製造例１の光輝性有色顔料を用い、表１〜２の処方で顔料を撹拌機で均一に分散させて可変光輝性組成物を調製した。
この組成物をドクターブレードを用いて白紙上に塗布した。得られた色紙を乾燥後、２０×１００ｍｍの大きさに切り取り、測定用試料とした。測色は肉眼観察と、村上色彩研究所製の変角分光測色機（ＧＣＭＳ−３）を用いた測色（入射角４５℃、受光角３５度及び６５℃）を行った。各受光角における明度（Ｙ値）を光沢度とした。なお、測定用試料の乾燥後の塗膜膜厚は０．０１６ｍｍ及び０．０３２ｍｍの２種類であった。
【００２０】
【表１】
表１のインキ組成物の各受光角におけるＹ値をプロットしたものが図１である。図１から解るように顔料のバインダー樹脂（ニトロセルロース）に対する割合が４倍量以上になると、３５度と６５度の何れの受光角においても塗膜の光沢度が低くなり、受光角度による光沢度の差（△Ｙ）も小さくなり、フリップフロップ効果を十分に得ることができない。このような光沢度及びフリップフロップ効果の低下は肉眼観察でも容易に確認することができた。
一方、顔料の配合量が樹脂に対して０．５倍量より少ない場合には、塗膜自体の隠蔽力が低下し、光沢度、△Ｙが小さくなる傾向が認められた。また、肉眼観察においても顔料の色調が希薄で下地の影響を強く受けていることがはっきりと認められた。
【００２２】
これに対して、顔料と樹脂の重量比が１：２〜３．５：１の場合には、鮮やかな、光沢に優れた金色の外観を示し、フリップフロップ効果も良好な試料が得らた。
このことは次のように推察できる。すなわち、組成物中のバインダー樹脂に対する顔料の割合が多い場合には、図２のように基材上に形成された塗装被膜中における顔料の割合が大きくなるために、多くの顔料が基材表面と平行に配向した状態で存在できない。このような顔料の存在状態においては、顔料表面で反射される反射光の反射角度の幅が広く、従って全体として光沢度は低く、また、観察角度による光沢度の差も小さくなる。
【００２３】
一方、顔料の配合量が樹脂に対して少ない場合には、図３のように塗装被膜中における顔料の割合が小さいために、顔料は基材表面と平行に配向した状態で存在することができるものの、顔料間の間隔が大きい。そのために隠蔽力が低下するととも、反射光量が少ないために光沢度や△Ｙの値も小さくなる。
これに対して、組成物中の顔料とバインダー樹脂の配合割合が好適な範囲にある場合には、図４に示すように基材表面に形成された塗装被膜中においてほとんどの顔料が顔料が基材表面と平行に配向した状態で存在することができ、しかも顔料間の間隔も密で幾層にも積層して存在することができる。このような存在状態においては反射光の光量が十分で、顔料表面での反射光の反射角度も幅が狭いので、高い光沢度とともに優れたフリップフロップ効果を得ることができるものと考えられる。
【００２４】
以上のことから、本発明の可変光輝性組成物における好適な光輝性有色顔料：バインダー樹脂の重量比としては１：２〜３．５：１の範囲であることが理解される。
【００２５】
試験例２：塗装膜厚
次に、塗布膜厚を変えてその塗膜の外観、光沢度、フリップフロップ効果について肉眼で比較した。用いた可変光輝性組成物は前記表１の顔料濃度５重量％及び３０重量％のものである。
【００２６】
【表２】
【表３】
表２〜３からわかるように、塗膜膜厚が１０μｍ未満の場合には顔料による外観色が希薄で隠蔽力が低く、よって十分な色調や光沢度が得られず、フリップフロップ効果も小さい。一方、塗布膜厚が１００μｍ付近まで大きくなると塗膜がうまくのらずにまだらになることがあり、外観が不均一となりやすく、光沢度やフリップフロップ効果も低下する傾向にある。従って本発明の顔料組成物の塗装体において塗膜の膜厚は１０〜７０μｍが好適であることが理解される。
【００２９】
【実施例】
以下、さらに本発明の実施例を挙げるが、本発明はこれらによって限定されるものではない。なお、特に限定のない限り、配合量は重量％で表す。
【００３０】
実施例１ グラビアインキ
光輝性有色顔料 ３０．０％
エチレン−酢酸ビニル共重合樹脂 ７．５
塩素化ポリプロピレン ５．５
トルエン ２８．０
酢酸エチル ８．５
メチルエチルケトン １７．０
イソプロピルアルコール ２．５
ポリエチレンワックス ０．８
静電防止剤 ０．２
【００３１】
顔料は特願昭６１−１８８８８７号実施例１に記載の方法で製造した青色の光輝性顔料（被覆金属：コバルト）を用いた。各成分を混合し、混合物をサンドミルで混練してグラビアインキを得た。塗膜膜厚（乾燥後）６０μｍで白紙上にグラビア印刷を行ったところ、塗装体は青色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００３２】
実施例２ グラビアインキ
光輝性有色顔料 １５．０％
ポリアミド樹脂 １５．０
ロジンエステル ４．０
ニトロセルロース ３．０
イソプロピルアルコール ４６．０
酢酸エチル ５．０
トルエン １０．０
ポリエチレンワックス ２．０
【００３３】
顔料は特願昭６１−１８８８８７号実施例２に記載の方法で製造した緑色の光輝性顔料（被覆金属：ニッケル）を用いた。各成分を混合し、混合物をサンドミルで混練してグラビアインキを得た。塗膜膜厚（乾燥後）５０μｍでポリエチレンフィルム上にグラビア印刷を行ったところ、塗装体は緑色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００３４】
実施例３ グラビアインキ
光輝性有色顔料 ２０．０％
硬化ロジン １５．０
石油系樹脂 １０．０
トルエン ５５．０
【００３５】
顔料は被覆金属としてスズを用い、特願昭６１−１８８８８７号に記載の方法に準じて製造した。すなわち、Ｉｒｉｏｄｉｎ２１７（赤色の干渉色を有する雲母チタン、***Ｍｅｒｃｋ社製）５０ｇを８×１０−３Ｍ塩化スズ水溶液５００ｍｌに分散させ、濾過後、５×１０−４Ｍ塩化パラジウム水溶液に再度分散させた。濾過後、得られた活性化雲母チタン５０ｇを、浴温を室温に保った塩化スズ（ＩＩ）（６ｇ／ｌ）、チオ尿素（５５ｇ／ｌ）、酒石酸（３９ｇ／ｌ）からなる無電解スズメッキ浴５００ｍｌに分散させ、１時間撹拌を続けた。濾過後、水洗し、１５０℃で乾燥させ、赤色の鮮やかな外観色と干渉色を有する光輝性有色顔料５０．１ｇを得た。なお、得られた顔料は雲母１００重量部に対して５．１重量部のスズを含有していた。
【００３６】
得られた赤色の光輝性顔料を用い、上記の処方で各成分を混合し、混合物をサンドミルで混練してグラビアインキを得た。塗膜膜厚（乾燥後）６０μｍで白紙上にグラビア印刷を行ったところ、塗装体は赤色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００３７】
実施例４ グラビアインキ
光輝性有色顔料 ３０．０％
ニトロセルロース １０．０
ブチルセルソルブ １０．０
ナフサ ２５．０
シクロヘキサン ２５．０
【００３８】
顔料は被覆金属として亜鉛を用い、特願昭６１−１８８８８７号に記載の方法に準じて製造した。すなわち、Ｉｒｉｏｄｉｎ２２５（青色の干渉色を有する雲母チタン、***Ｍｅｒｃｋ社製）５０ｇを８×１０−３Ｍ塩化スズ水溶液５００ｍｌに分散させ、濾過後、５×１０−４Ｍ塩化パラジウム水溶液に再度分散させた。濾過後、得られた活性化雲母チタン５０ｇを、ｐＨ１１．５、浴温を８０〜９０℃室温に保ったシアン化亜鉛（６０ｇ／ｌ）、クエン酸ナトリウム（６０ｇ／ｌ）、次リン酸ナトリウム（６０ｇ／ｌ）シアン化ナトリウム（８０ｇ／ｌ）からなる無電解亜鉛メッキ浴５００ｍｌに分散させ、１時間撹拌を続けた。濾過後、水洗し、１５０℃で乾燥させ、青色の鮮やかな外観色と干渉色を有する光輝性有色顔料５２．２ｇを得た。なお、得られた顔料は雲母１００重量部に対して９．６重量部の亜鉛を含有していた。
【００３９】
得られた青色の光輝性顔料を用い、上記の処方で各成分を混合し、混合物をサンドミルで混練してグラビアインキを得た。塗膜膜厚（乾燥後）４０μｍで白紙上にグラビア印刷を行ったところ、塗装体は青色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００４０】
実施例５ グラビアインキ
光輝性有色顔料（製造例１） １４．０％
エチレン−酢酸ビニル共重合樹脂 ７．２
塩素化ポリプロピレン ５．８
トルエン ５８．０
酢酸エチル １１．０
イソプロピルアルコール ３．０
ポリエチレンワックス ０．８
静電防止剤 ０．２
【００４１】
各成分を混合し、混合物をサンドミルで混練してグラビアインキを得た。塗膜膜厚（乾燥後）６０μｍで白紙上にグラビア印刷を行ったところ、塗装体は金色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００４２】
実施例６ スクリーンインキ
光輝性有色顔料 １５．０％
アクリル樹脂 ２０．０
ナフサ ３５．０
ブチルセルソルブ ３０．０
【００４３】
顔料は特願昭６１−１８８８８７号実施例４に記載の方法で製造した赤紫色の光輝性顔料（被覆金属：コバルト）を用いた。上記処方でスクリーンインキを製造し、塗膜膜厚（乾燥後）６０μｍでＡＢＳ樹脂上にスクリーン印刷したところ、塗装体は赤紫色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００４４】
実施例７ スクリーンインキ
光輝性有色顔料 １５．０％
ニトロセルロース １５．０
シクロヘキサノン ４０．０
イソホロン １０．０
ナフサ １０．０
ジブチルフタレート １０．０
【００４５】
顔料は特願昭６１−１８８８８７号実施例３に記載の方法で製造した青色の光輝性顔料（金属として銅使用）を用いた。上記処方でスクリーンインキを製造し、塗膜膜厚（乾燥後）６０μｍでセルロイドフィルム上にスクリーン印刷したところ、塗装体は青色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００４６】
実施例８ スクリーンインキ
光輝性有色顔料 ２０．０％
ニトロセルロース ２０．０
シクロヘキサノン ４５．０
イソホロン １０．０
ジオクチルフタレート ５．０
【００４７】
顔料は被覆金属として金を用い、特願昭６１−１８８８８７号に記載の方法に準じて製造した。すなわち、雲母５０ｇをイオン交換水５０ｇに添加して十分に撹拌し均一に分散させた。得られた分散液に濃度４０重量％の硫酸チタニル水溶液１５０．０ｇを加えて撹拌しながら加熱し３時間沸騰させた。放冷後、濾過水洗し、９００℃で乾燥して二酸化チタン被覆雲母（雲母チタン）７８ｇを得た。
【００４８】
得られた雲母チタン５０ｇを８×１０−３Ｍ塩化スズ水溶液５００ｍｌに分散させ、濾過後、５×１０−４Ｍ塩化パラジウム水溶液に再度分散させた。濾過後、得られた活性化雲母チタン５０ｇを、ｐＨ７．０〜７．５、浴温を９２〜９５℃に保った、カリウム（２ｇ／ｌ）、塩化アンモニウム（７５ｇ／ｌ）、シュウ酸ナトリウム（５０ｇ／ｌ）、亜リン酸ナトリウム（５０ｇ／ｌ）からなる無電解金メッキ浴１４００ｍｌに分散させ、１時間撹拌を続けた。濾過後、水洗し、１２０℃で乾燥させ、金色の鮮やかな外観色と干渉色を有する光輝性有色顔料５３．２ｇを得た。なお、得られた顔料は雲母１００重量部に対して７．１重量部の金を含有していた。
【００４９】
得られた金色の光輝性顔料を用い、上記の処方でスクリーンインキを得た。塗膜膜厚（乾燥後）６０μｍで塩化ビニール上にスクリーン印刷を行ったところ、塗装体は青色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００５０】
実施例９ スクリーンインキ
光輝性有色顔料 １５．０％
アクリル樹脂 ２０．０
ナフサ ３５．０
ブチルセルソルブ ３０．０
【００５１】
顔料は被覆金属として銀を用い、特願昭６１−１８８８８７号に記載の方法に準じて製造した。すなわち、Ｉｒｉｏｄｉｎ１０１（銀色の干渉色を有する雲母チタン、***Ｍｅｒｃｋ社製）５０ｇを８×１０−３Ｍ塩化スズ水溶液５００ｍｌに分散させ、濾過後、５×１０−４Ｍ塩化パラジウム水溶液に再度分散させた。濾過後、得られた活性化雲母チタン５０ｇを、浴温を２０℃室温に保った硝酸銀（５ｇ）、水（７０ｍｌ）、３８％ホルマリン（９ｍｌ）からなる無電解銀メッキ浴に分散させた。濾過後、水洗し、１２０℃で乾燥させ、銀色の鮮やかな外観色と干渉色を有する光輝性有色顔料５２．４ｇを得た。なお、得られた顔料は雲母１００重量部に対して４．４重量部の銀を含有していた。
【００５２】
得られた銀色の光輝性顔料を用い、上記処方でスクリーンインキを製造し、塗膜膜厚（乾燥後）５０μｍでＡＢＳ樹脂上にスクリーン印刷したところ、塗装体は銀色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００５３】
実施例１０ スクリーンインキ
光輝性有色顔料 １５．０％
アクリル樹脂 ２０．０
ナフサ ３５．０
ブチルセルソルブ ３０．０
【００５４】
顔料は特願昭６１−１８８８８７号に記載の方法に準じて製造した。すなわち、実施例１で用いた青色の光輝性有色顔料（被覆金属：コバルト）５０ｇを用いて、実施例９の方法と同様にして銀を被覆し、青色の鮮やかな外観色と干渉色を有する光輝性有色顔料５１．０ｇを得た。なお、得られた顔料は雲母１００重量部に対して４．２重量部の銀を含有していた。
得られた青色の光輝性顔料を用い、上記処方でスクリーンインキを製造し、塗膜膜厚（乾燥後）５０μｍでＡＢＳ樹脂上にスクリーン印刷したところ、塗装体は青色の良好な色調と光沢度を発揮し、また、見る角度によって光沢度が異なるフリップフロップ効果が得られた。
【００５５】
【発明の効果】
以上のように、本発明に係る可変光輝性組成物は光輝性有色顔料とバインダー樹脂の重量比を１：２〜３．５：１の範囲とし、乾燥後の塗膜膜厚を０．０１〜０．０７ｍｍとすることにより、鮮やかな有色の外観色と高い光沢度とともに、フリップフロップ効果を得ることができる。
【図面の簡単な説明】
【図１】本発明の一実施例に係る可変光輝性組成物中の顔料濃度による光沢度の変化を示す図である。
【図２】本発明の一実施例に係る可変光輝性組成物中の顔料と樹脂の配合比率によるその塗装被膜中の顔料の存在状態を示す図である。
【図３】本発明の一実施例に係る可変光輝性組成物中の顔料と樹脂の配合比率によるその塗装被膜中の顔料の存在状態を示す図である。
【図４】本発明の一実施例に係る可変光輝性組成物中の顔料と樹脂の配合比率によるその塗装被膜中の顔料の存在状態を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a brilliant composition, particularly to a composition that provides variable brilliancy whose brilliancy changes depending on an observation angle, its coated body, its coating method, and the like.
[0002]
[Prior art]
2. Description of the Related Art In paints and printing inks, it is often required to give a part or all of a base material a beautiful appearance and to give it a glittering effect to give a sense of quality. 2. Description of the Related Art Conventionally, metal powders such as aluminum powder, titanium mica-based pearl pigments, and the like have been generally used by being dispersed and mixed in paints and ink compositions in order to impart glitter to painted and printed materials.
[0003]
[Problems to be solved by the invention]
However, for example, in a method using such a metal powder or the like, the luster may become dull with the lapse of time due to corrosion or a change in orientation due to a high specific gravity. Due to the color, the metallic powder alone could not obtain a colored glitter such as red or blue.
On the other hand, mica titanium-based pearl pigments are known to have various colored interference colors, but the appearance color of such pearl pigments is basically white, and its brilliantness is also high. It was a pearl-like mat and was not satisfactory in applications where a vivid colored appearance and high glossiness were desired.
[0004]
In addition, in terms of brilliancy, a flip-flop effect is often required in which the gloss differs significantly depending on the observation angle. However, the conventional method exhibits a bright colored appearance color and a high gloss, and exhibits the flip-flop effect. However, it was difficult to obtain a high coated body.
The present invention has been made in view of such problems of the prior art, and an object thereof is to provide a vivid colored appearance color and high glitter, and furthermore, a variable glitter composition having a high flip-flop effect. Is to provide.
[0005]
[Means for Solving the Problems]
The present inventors have obtained pigments obtained by previously coating the surface of titanium dioxide-coated mica with one or more metal particles selected from cobalt, nickel, and copper, as well as a brilliant color with various colored appearance colors. (Japanese Patent Application No. 61-188887). Then, it has been found that a coated body of a composition such as a paint or an ink containing the pigment properly exhibits a good colored glitter, and that the glossiness changes remarkably depending on an observation angle. Further, they have also found that the same effect can be obtained when zinc, tin, gold, and silver are used as the coating metal, and have completed the present invention.
[0006]
That is, in the variable glitter composition according to claim 1 of the present invention, the surface of the titanium dioxide-coated mica is one or more metal particles selected from cobalt, nickel, copper, zinc, tin, gold, and silver. Contains a brilliant colored pigment that is coated and has a metal coating amount of 1 to 60 parts by weight with respect to 100 parts by weight of mica, a binder resin, and an organic solvent.AndIt is characterized in that the blending ratio of the brilliant colored pigment and the binder resin is in the range of 1: 2 to 3.5: 1 by weight.
[0007]
Claims of the invention2The variable glittering coating body described in claim1A coated body in which the variable glitter composition according to the above is applied on a substrate, wherein the weight ratio of the glitter colored pigment to the binder resin in the dried coating film of the variable glitter composition is 1: 2 to 3. 0.5: 1.
[0008]
Claims of the invention3The variable glittering coating body described in claim2The coated body according to the above, characterized in that the geometric thickness of the coating film after drying the variable glitter composition is in the range of 0.01 to 0.07 mm.
Claims of the invention4The method described in the claims1The above-described variable glitter composition is coated on a substrate such that the geometric layer thickness of the variable glitter composition after drying is in the range of 0.01 to 0.07 mm.
[0009]
[Embodiment of the present invention]
Hereinafter, embodiments of the present invention will be described in detail.
The brilliant colored pigment used in the present invention is basically the one described in Japanese Patent Application No. 188888/1986, and the production method thereof can be the method described in Japanese Patent Application No. 188888/1986. In addition, when using zinc, tin, gold, and silver in addition to cobalt, nickel, and copper as the metal species that coats the surface of the titanium dioxide-coated mica, a brilliant colored pigment having a colored appearance color and glossiness is similarly obtained. It turns out that it can. Therefore, the glittering colored pigment used in the present invention has a mica surface coated with titanium dioxide, and the titanium dioxide-coated mica surface further includes one or more selected from cobalt, nickel, copper, zinc, tin, gold, and silver. It is coated with two or more kinds of metal particles, and the metal coating amount is 1 to 60 parts by weight based on 100 parts by weight of mica.
[0010]
This brilliant colored pigment has a vivid chromatic appearance color, despite being basically composed of an achromatic inorganic raw material such as mica, titanium dioxide and metal, and has excellent glossiness. Things. Also, unlike coloring pigments made of organic pigments, they have very good pigment properties such as stability.
The blending amount of the glittering colored pigment in the variable glittering composition of the present invention is not particularly limited, but is usually preferably from 5 to 35% by weight based on the total amount of the composition. If the blending amount of the pigment is small, the hiding power is reduced, and if the blending amount is excessive, the dispersion of the pigment in the variable glitter composition becomes uneven, or the appearance of the composition coated body becomes mottled, The viscosity of the material may increase, which may have an unfavorable effect on workability, printability, and the like.
[0011]
In the present invention, the variable glitter composition refers to a composition for coloring or glossing a part of or the entire surface of a substrate, and is, for example, a composition such as a paint or a printing ink. . The substrate coated with the variable glitter composition is not particularly limited as long as it is a substrate that requires variable glitter, such as paper, paperboard, cloth, leather, metal, plastic, etc., and its shape is also various. Applicable. Of course, a substrate that has been previously painted, printed, or coated may be used.
[0012]
The binder resin to be blended in the variable glitter composition according to the present invention is a resin capable of stably adhering a glitter pigment to a substrate, and after coating the variable glitter composition on a substrate, A film is formed on a substrate in a state in which the solvent in the composition is volatilized and the glittering colored pigment is embedded. The binder resin is not particularly limited because it is selected according to the compatibility with the base material, the strength of the formed film, the thickness of the film, and the like. However, those usually used as binders for paints and printing inks can be used. For example, Gilsonite, maleic acid resin, cyclized rubber, cured rosin, petroleum resin, nitrocellulose, acrylic resin, polyurethane resin, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride , Polyester resin, alkyd resin, linseed oil, modified phenol resin, fumaric acid resin, epoxy ester resin, epoxy amino resin, epoxy phenol resin, polyester resin, vinyl resin, polyamide resin, mineral varnish, ketone resin, chloride rubber, ethyl cellulose, Urea resins, melamine resins and the like can be mentioned.
[0013]
Further, as the solvent to be blended in the variable glitter composition according to the present invention, it is possible to use a solvent generally used for paints and inks, usually improves the workability by dissolving the binder resin well, In addition, there is no particular limitation as long as the brilliant colored pigment can be well dispersed and compounded in the resin solution. For example, toluene, xylene, n-hexane, cyclohexane, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol Isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, and the like.
[0014]
As the solvent, a volatile organic solvent is often used, but in some cases, water or the like may be blended.
In the variable glitter composition of the present invention, in order to adjust the properties of the composition as long as the effects of the present invention are not impaired, various additives usually added to paints and inks in addition to the essential components described above are used. You may mix. Examples include plasticizers, waxes, wetting agents, stabilizers, dyes and pigments, antistatic agents, defoamers, antioxidants, leveling agents, polymerization inhibitors, filler agents, and the like.
[0015]
In the present invention, the weight ratio of the glittering colored pigment to the binder resin in the variable glittering composition is 1: 2 to 3 in order to obtain a highly colored glitter and a flip-flop effect in which the gloss changes significantly depending on the viewing direction. .5: 1. When such a variable glitter composition is coated on a substrate, the solvent in the variable glitter composition volatilizes upon drying, and a binder resin film is formed on the substrate, and the glitter colored pigment is retained in this film. Thus, a coating film is formed. Therefore, the weight ratio of the bright colored pigment to the binder resin in the coating film on the substrate is in the range of 1: 2 to 3.5: 1. A coating film having such a composition ratio gives a substrate a colored appearance color and a high glitter, and exhibits a good flip-flop effect.
[0016]
Moreover, in the coated body in which the variable glitter composition according to the present invention is coated on a substrate, it is preferable that the geometric film thickness of the dried coating film is 0.01 to 0.07 mm.
When the coating film thickness is small, the appearance color of the pigment is dilute and the hiding power is low, and sufficient color tone, glossiness and flip-flop effect cannot be obtained. On the other hand, if the coating film thickness is too large, the coating film may be unsatisfactory and may be mottled, the appearance tends to be uneven, and the glossiness and the flip-flop effect tend to decrease.
[0017]
The coating method in the present invention is a method of applying the variable glitter composition according to the present invention to a part or the whole surface of a substrate, and is a concept including a general printing method. As the coating method of the present invention, conventionally used coating methods, printing methods, and coating techniques can be used. For example, the printing methods include convex plate printing, concave plate printing, gravure printing, screen printing, and flexographic printing. , Offset printing, ink jet printing, electrostatic printing and the like can be used. Further, coating methods such as brush coating, spray coating, rolling coating, stencil coating, electrostatic coating, flow coating, dip coating, roller coating, and spray coating can also be used.
Hereinafter, the present invention will be described in more detail with reference to specific examples.
[0018]
Production Example 1 Production of brilliant colored pigment
50 g of Iriodin 205 (rutile mica titanium having a golden interference color, manufactured by Merck, West Germany) was dispersed in 500 ml of an 8 × 10 −3 M aqueous solution of tin chloride, filtered, and then dispersed again in an aqueous solution of 5 × 10 −3 M palladium chloride. After filtration, 50 g of the activated titanium mica thus obtained was maintained at pH 6 to 6.5 and a bath temperature of 80 ° C., sodium hypophosphite (10 g / l), sodium citrate (100 g / l), and ammonium sulfate (50 g / l). ) And nickel sulfate (11.75 g / l) in an electroless nickel plating bath (1200 ml), and stirring was continued for 1 hour. After filtration, washing with water and drying at 150 ° C. for 12 hours, 52 g of a brilliant colored pigment having a golden appearance color was obtained.
[0019]
Test Example 1: Ratio of pigment to resin
Using the brilliant colored pigment of Production Example 1, the pigment was uniformly dispersed with a stirrer according to the formulations shown in Tables 1 and 2, thereby preparing a variable brilliant composition.
This composition was applied on white paper using a doctor blade. After drying the obtained colored paper, it was cut into a size of 20 × 100 mm to obtain a measurement sample. The colorimetry was performed by visual observation and colorimetry (incident angle 45 ° C., light receiving
[0020]
[Table 1]
FIG. 1 is a plot of the Y value at each light receiving angle of the ink composition in Table 1. As can be seen from FIG. 1, when the ratio of the pigment to the binder resin (nitrocellulose) is 4 times or more, the glossiness of the coating film decreases at any of the light receiving angles of 35 degrees and 65 degrees, and the glossiness according to the light receiving angle is reduced. , The difference (ΔY) becomes small, and a sufficient flip-flop effect cannot be obtained. Such a decrease in the gloss and the flip-flop effect could be easily confirmed by visual observation.
On the other hand, when the amount of the pigment was less than 0.5 times the amount of the resin, the hiding power of the coating film itself was reduced, and the glossiness and ΔY tended to be reduced. In addition, it was clearly observed by visual observation that the color tone of the pigment was weak and strongly affected by the background.
[0022]
On the other hand, when the weight ratio of the pigment to the resin was 1: 2 to 3.5: 1, a sample having a vivid and glossy gold appearance and a good flip-flop effect was obtained. .
This can be inferred as follows. That is, when the proportion of the pigment to the binder resin in the composition is large, the proportion of the pigment in the coating film formed on the substrate as shown in FIG. Cannot exist in a state of being oriented in parallel with In the presence state of such a pigment, the reflection angle of the reflected light reflected on the pigment surface is wide, so that the glossiness is low as a whole, and the difference in the glossiness depending on the observation angle is small.
[0023]
On the other hand, when the amount of the pigment is small relative to the resin, the pigment can exist in a state of being oriented parallel to the substrate surface because the proportion of the pigment in the coating film is small as shown in FIG. However, the distance between the pigments is large. As a result, the hiding power is reduced, and the gloss and the value of ΔY are also reduced due to the small amount of reflected light.
On the other hand, when the blending ratio of the pigment and the binder resin in the composition is within a suitable range, most of the pigment is based on the pigment in the coating film formed on the substrate surface as shown in FIG. The pigments can exist in a state of being oriented parallel to the material surface, and the spacing between the pigments can be close, and the pigments can exist in layers. In such a state, since the amount of reflected light is sufficient and the angle of reflection of the reflected light on the pigment surface is narrow, it is considered that an excellent flip-flop effect as well as high gloss can be obtained.
[0024]
From the above, it is understood that the preferable weight ratio of the brilliant colored pigment to the binder resin in the variable brilliant composition of the present invention is in the range of 1: 2 to 3.5: 1.
[0025]
Test example 2: Paint film thickness
Next, the coating film thickness was changed and the appearance, glossiness and flip-flop effect of the coating film were compared with the naked eye. The variable glitter composition used had a pigment concentration of 5% by weight and 30% by weight in Table 1 above.
[0026]
[Table 2]
[Table 3]
As can be seen from Tables 2 and 3, when the thickness of the coating film is less than 10 μm, the appearance color of the pigment is dilute and the hiding power is low, so that a sufficient color tone and glossiness cannot be obtained, and the flip-flop effect is also small. On the other hand, when the coating film thickness is increased to around 100 μm, the coating film may be unsatisfactory and may be mottled, the appearance tends to be uneven, and the glossiness and the flip-flop effect tend to decrease. Therefore, it is understood that the thickness of the coating film in the coated body of the pigment composition of the present invention is preferably from 10 to 70 μm.
[0029]
【Example】
Hereinafter, examples of the present invention will be further described, but the present invention is not limited thereto. Unless otherwise specified, the amount is expressed in% by weight.
[0030]
Example 1 Gravure ink
Bright colored pigment 30.0%
Ethylene-vinyl acetate copolymer resin 7.5
5.5 chlorinated polypropylene
Toluene 28.0
Ethyl acetate 8.5
Methyl ethyl ketone 17.0
Isopropyl alcohol 2.5
Polyethylene wax 0.8
Antistatic agent 0.2
[0031]
As the pigment, a blue brilliant pigment (coated metal: cobalt) produced by the method described in Example 1 of Japanese Patent Application No. 61-188888 was used. Each component was mixed, and the mixture was kneaded with a sand mill to obtain a gravure ink. When gravure printing was performed on white paper with a coating film thickness (after drying) of 60 μm, the coated body exhibited a good color tone and glossiness of blue, and a flip-flop effect in which the glossiness varied depending on the viewing angle was obtained. Was.
[0032]
Example 2 Gravure ink
Bright colored pigment 15.0%
Polyamide resin 15.0
Rosin ester 4.0
Nitrocellulose 3.0
Isopropyl alcohol 46.0
Ethyl acetate 5.0
Toluene 10.0
Polyethylene wax 2.0
[0033]
As the pigment, a green glittering pigment (coated metal: nickel) produced by the method described in Example 2 of Japanese Patent Application No. 61-188888 was used. Each component was mixed, and the mixture was kneaded with a sand mill to obtain a gravure ink. When gravure printing was performed on a polyethylene film with a coating film thickness (after drying) of 50 μm, the painted body exhibited a good color tone and glossiness of green, and a flip-flop effect in which the glossiness varied depending on the viewing angle was obtained. Was done.
[0034]
Example 3 Gravure ink
Bright colored pigment 20.0%
Cured rosin 15.0
Petroleum resin 10.0
Toluene 55.0
[0035]
The pigment was produced using tin as a coating metal according to the method described in Japanese Patent Application No. 188888/1986. That is, 50 g of Iriodin 217 (mica titanium having a red interference color, manufactured by Merck, West Germany) is 8 × 10-3After dispersing in 500 ml of M tin chloride aqueous solution and filtering, 5 × 10-4It was redispersed in an aqueous M palladium chloride solution. After filtration, 50 g of the activated titanium mica thus obtained was subjected to electroless tin plating comprising tin (II) chloride (6 g / l), thiourea (55 g / l), and tartaric acid (39 g / l) while maintaining the bath temperature at room temperature. Dispersed in 500 ml of bath and continued stirring for 1 hour. After filtration, washing with water and drying at 150 ° C., 50.1 g of a brilliant colored pigment having a vivid red appearance color and interference color was obtained. The obtained pigment contained 5.1 parts by weight of tin with respect to 100 parts by weight of mica.
[0036]
Using the obtained red glittering pigment, the respective components were mixed according to the above-mentioned formulation, and the mixture was kneaded with a sand mill to obtain a gravure ink. When gravure printing was performed on white paper with a coating film thickness (after drying) of 60 μm, the coated body exhibited good red color tone and glossiness, and a flip-flop effect with glossiness varying with the viewing angle was obtained. Was.
[0037]
Example 4 Gravure ink
Bright colored pigment 30.0%
Nitrocellulose 10.0
Butyl Cellsolve 10.0
Naphtha 25.0
Cyclohexane 25.0
[0038]
The pigment was produced according to the method described in Japanese Patent Application No. 61-1888887 using zinc as a coating metal. That is, 50 g of Iriodin 225 (mica titanium having a blue interference color, manufactured by Merck, West Germany) is 8 × 10-3After dispersing in 500 ml of M tin chloride aqueous solution and filtering, 5 × 10-4It was redispersed in an aqueous M palladium chloride solution. After filtration, 50 g of the activated titanium mica thus obtained was applied to zinc cyanide (60 g / l), sodium citrate (60 g / l), sodium hypophosphate having a pH of 11.5 and a bath temperature of 80 to 90 ° C. at room temperature. (60 g / l) Dispersed in 500 ml of an electroless galvanizing bath made of sodium cyanide (80 g / l), and stirring was continued for 1 hour. After filtration, washing with water and drying at 150 ° C. were obtained 52.2 g of a brilliant colored pigment having a vivid blue external color and an interference color. The obtained pigment contained 9.6 parts by weight of zinc with respect to 100 parts by weight of mica.
[0039]
Using the obtained blue glittering pigment, the respective components were mixed according to the above-mentioned formulation, and the mixture was kneaded with a sand mill to obtain a gravure ink. When gravure printing was performed on white paper with a coating film thickness (after drying) of 40 μm, the coated body exhibited a good blue color tone and glossiness, and a flip-flop effect with glossiness varying with the viewing angle was obtained. Was.
[0040]
Example 5 Gravure ink
Bright colored pigment (Production Example 1) 14.0%
Ethylene-vinyl acetate copolymer resin 7.2
Chlorinated polypropylene 5.8
Toluene 58.0
Ethyl acetate 11.0
Isopropyl alcohol 3.0
Polyethylene wax 0.8
Antistatic agent 0.2
[0041]
Each component was mixed, and the mixture was kneaded with a sand mill to obtain a gravure ink. When gravure printing was performed on white paper with a coating film thickness (after drying) of 60 μm, the coated body exhibited a good golden color tone and glossiness, and a flip-flop effect with glossiness varying with the viewing angle was obtained. Was.
[0042]
Example 6 Screen ink
Bright colored pigment 15.0%
Acrylic resin 20.0
Naphtha 35.0
Butyl Cellsolve 30.0
[0043]
The pigment used was a red-violet brilliant pigment (coated metal: cobalt) produced by the method described in Example 4 of Japanese Patent Application No. 61-188887. A screen ink was manufactured according to the above formulation and screen-printed on an ABS resin with a coating film thickness (after drying) of 60 μm. The coated body exhibited a good red-purple color tone and glossiness, and showed a gloss depending on the viewing angle. Different degrees of flip-flop effects were obtained.
[0044]
Example 7 Screen ink
Bright colored pigment 15.0%
Nitrocellulose 15.0
Cyclohexanone 40.0
Isophorone 10.0
Naphtha 10.0
Dibutyl phthalate 10.0
[0045]
As the pigment, a blue brilliant pigment (using copper as a metal) manufactured by the method described in Example 3 of Japanese Patent Application No. 61-188888 was used. A screen ink was manufactured according to the above formula and screen-printed on a celluloid film with a coating film thickness (after drying) of 60 μm. The coated body exhibited a good blue color tone and glossiness, and the glossiness depended on the viewing angle. Have different flip-flop effects.
[0046]
Example 8 Screen ink
Bright colored pigment 20.0%
Nitrocellulose 20.0
Cyclohexanone 45.0
Isophorone 10.0
Dioctyl phthalate 5.0
[0047]
The pigment was produced according to the method described in Japanese Patent Application No. 188888/1986 using gold as the coating metal. That is, 50 g of mica was added to 50 g of ion-exchanged water, sufficiently stirred, and uniformly dispersed. 150.0 g of an aqueous solution of titanyl sulfate having a concentration of 40% by weight was added to the obtained dispersion, and the mixture was heated with stirring and boiled for 3 hours. After cooling, the mixture was filtered, washed with water, and dried at 900 ° C. to obtain 78 g of mica (titanium mica) coated with titanium dioxide.
[0048]
50 g of the obtained mica titanium is 8 × 10-3After dispersing in 500 ml of M tin chloride aqueous solution and filtering, 5 × 10-4It was redispersed in an aqueous M palladium chloride solution. After filtration, potassium (2 g / l), ammonium chloride (75 g / l), sodium oxalate, and 50 g of the activated titanium mica obtained were maintained at pH 7.0 to 7.5 and a bath temperature of 92 to 95 ° C. (50 g / l) and 1400 ml of an electroless gold plating bath composed of sodium phosphite (50 g / l), and stirring was continued for 1 hour. After filtration, washing with water and drying at 120 ° C. were obtained 53.2 g of a brilliant colored pigment having a vivid golden outer color and interference color. Incidentally, the obtained pigment contained 7.1 parts by weight of gold with respect to 100 parts by weight of mica.
[0049]
Using the obtained golden glittering pigment, a screen ink was obtained with the above formulation. Screen printing on vinyl chloride with a coating film thickness (after drying) of 60 μm shows that the coated body exhibits a good blue color tone and gloss, and that the flip-flop effect varies in gloss depending on the viewing angle. Was done.
[0050]
Example 9 Screen ink
Bright colored pigment 15.0%
Acrylic resin 20.0
Naphtha 35.0
Butyl Cellsolve 30.0
[0051]
The pigment was produced using silver as a coating metal according to the method described in Japanese Patent Application No. 61-1888887. That is, 50 g of Iriodin 101 (titanium mica having a silver interference color, manufactured by Merck, West Germany) is 8 × 10-3After dispersing in 500 ml of M tin chloride aqueous solution and filtering, 5 × 10-4It was redispersed in an aqueous M palladium chloride solution. After filtration, 50 g of the activated titanium mica obtained was dispersed in an electroless silver plating bath composed of silver nitrate (5 g), water (70 ml), and 38% formalin (9 ml), which was kept at a bath temperature of 20 ° C. and room temperature. After filtration, washing with water and drying at 120 ° C. were obtained 52.4 g of a brilliant colored pigment having a vivid silver appearance color and interference color. The obtained pigment contained 4.4 parts by weight of silver with respect to 100 parts by weight of mica.
[0052]
Using the obtained silver glittering pigment, a screen ink was manufactured according to the above formulation, and screen-printed on an ABS resin with a coating film thickness (after drying) of 50 μm. The coated body had a good silver color tone and gloss. And a flip-flop effect of varying gloss depending on the viewing angle was obtained.
[0053]
Example 10 Screen ink
Bright colored pigment 15.0%
Acrylic resin 20.0
Naphtha 35.0
Butyl Cellsolve 30.0
[0054]
The pigment was produced according to the method described in Japanese Patent Application No. 188888/1986. That is, silver was coated in the same manner as in Example 9 using 50 g of the blue brilliant colored pigment (coated metal: cobalt) used in Example 1, and had a vivid appearance color and interference color of blue. 51.0 g of bright colored pigment was obtained. The pigment thus obtained contained 4.2 parts by weight of silver with respect to 100 parts by weight of mica.
Using the obtained blue glittering pigment, a screen ink was manufactured according to the above formulation and screen-printed on an ABS resin with a coating film thickness (after drying) of 50 μm. The coated body had a good blue color tone and gloss. And a flip-flop effect of varying gloss depending on the viewing angle was obtained.
[0055]
【The invention's effect】
As described above, the variable glitter composition according to the present invention has a glitter colored pigment and a binder resin in a weight ratio of 1: 2 to 3.5: 1 and a dried coating film thickness of 0.01. By setting the thickness to 0.07 mm, a flip-flop effect can be obtained together with a vivid colored appearance color and high glossiness.
[Brief description of the drawings]
FIG. 1 is a graph showing a change in glossiness according to a pigment concentration in a variable glitter composition according to one embodiment of the present invention.
FIG. 2 is a view showing the state of the pigment in the coating film according to the mixing ratio of the pigment and the resin in the variable glitter composition according to one embodiment of the present invention.
FIG. 3 is a view showing the state of the pigment in the coating film according to the mixing ratio of the pigment and the resin in the variable glitter composition according to one embodiment of the present invention.
FIG. 4 is a view showing the state of pigment present in a coating film according to the mixing ratio of pigment and resin in the variable glitter composition according to one embodiment of the present invention.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33779795A JP3588513B2 (en) | 1995-12-01 | 1995-12-01 | Variable glitter composition, coated body and coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33779795A JP3588513B2 (en) | 1995-12-01 | 1995-12-01 | Variable glitter composition, coated body and coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09157557A JPH09157557A (en) | 1997-06-17 |
| JP3588513B2 true JP3588513B2 (en) | 2004-11-10 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33779795A Expired - Fee Related JP3588513B2 (en) | 1995-12-01 | 1995-12-01 | Variable glitter composition, coated body and coating method |
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| Country | Link |
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| JP (1) | JP3588513B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6129784A (en) * | 1997-09-30 | 2000-10-10 | Shiseido Co., Ltd. | Color titanated mica pigment and coated-body using the same |
| JP2003003089A (en) * | 2001-06-26 | 2003-01-08 | Kao Corp | Covered powder |
| JP2005234045A (en) * | 2004-02-17 | 2005-09-02 | Fujifilm Electronic Materials Co Ltd | Color resin composition |
| JP2012193250A (en) * | 2011-03-15 | 2012-10-11 | Toyo Ink Sc Holdings Co Ltd | Ink composition |
| KR101551657B1 (en) * | 2013-10-28 | 2015-09-09 | 씨큐브 주식회사 | Method of manufacturing pigment with excellent electrical conductivity and corrosion resistance |
| JP7205757B2 (en) * | 2019-01-11 | 2023-01-17 | 株式会社リコー | Recording liquid and printed matter |
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1995
- 1995-12-01 JP JP33779795A patent/JP3588513B2/en not_active Expired - Fee Related
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| JPH09157557A (en) | 1997-06-17 |
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