JP3621626B2

JP3621626B2 - Colored transparent inorganic coating composition, method for producing the same and method for coating the composition

Info

Publication number: JP3621626B2
Application number: JP2000117112A
Authority: JP
Inventors: ジョン−ハキム; ヒョン−ジュンパク; ヨン−ジンリ
Original assignee: Individual
Current assignee: Individual
Priority date: 1999-12-22
Filing date: 2000-04-18
Publication date: 2005-02-16
Anticipated expiration: 2020-04-18
Also published as: JP2001181572A; KR100374172B1; KR20010060425A

Description

【０００１】
【発明の属する技術分野】
本発明は着色透明無機塗料組成物とその製造方法及び組成物コーティング方法に関するもので、金属、プラスチック、ガラス、紙等基材表面に機能性着色機能を付与する着色透明無機塗料組成物とその製造方法及び組成物コーティング方法に関する。
【０００２】
【従来の技術】
一般的に、ステンレス，アルミニウム等の金属とセメント、ガラス、プラスチック、紙等の製品の表面に無機塗料をコーティング、硬化し美麗な美装性、耐熱性、耐候性、耐汚染性、高硬度、耐水性、密着性、遠赤外線放射性、耐蝕性、耐久性、耐冷熱性等を付与する機能性塗料は多用な分野に適用されている。
【０００３】
有色無機塗料（大韓民国特許公開９５−１８３６０、大韓民国特許公開９７−４２８６５、大韓民国特許出願９８−３１０８８、日本国特許公告昭５３−５０４２、日本国特許公開昭６３−７５０７３、日本国特許公開昭６３−８１１７６、日本国特許公開平１−１４９８６６）の場合、白色、黒色及びカラー三原色を基礎とするソリッドタイプと、ここに金属性色相を付与するメタリックタイプ等の塗料組成物を塗布し塗膜の耐熱、耐候性、耐久性をもつ塗料及びコーティング方法について紹介している。このソリッドタイプ及びメタリックタイプの無機塗料の場合、適用する素材、例えば、チタン・ステンレススチール・アルミニウムの表面の質感及び模様等をそのまま表現することが不可能な不透明性塗料である。
【０００４】
有機塗料としては、着色透明染料等を使用した有機透明着色塗料がある。これは、有機塗料としての特性である熱変色、低硬度、低耐候性、有機溶剤による溶解等を示し、火災時に有毒ガスを発生する等の低い物性で建築用内外装剤、各種素材の機能性表面塗装として適合しない。また、フッ素塗料の場合、他の有機塗料に比べて耐候性は優れているが、それ自体の結合力は共有結合に依存するため、金属素材との接着力がよくなくて金属に適用する場合、大部分エポキシ系またはアクリル系プライマを使用する。しかし、耐候性を必要とする建築用素材には、透明性プライマを使用し着色透明性フッ素塗料をチタン・ステンレススチール・アルミニウムのような金属素材に塗装するとしても、フッ素透明塗膜層を大部分は１００％が太陽光の紫外線（ＵＶ）が通過しプライマの有機ポリマーを破壊しＣＯ_２エステル類等の有機物に分解されて、フッ素塗料の塗膜を押出し最終的に変色及び塗膜剥離が発生する。もちろん、前記のような問題点を解決しようとフッ素塗料に紫外線吸収剤を添加したこともあるが、紫外線吸収剤も紫外線により分解されるため若干の遅延効果を与えるだけで長期間の耐候性を補償できず、火災時に発生され得る有毒性、長期間の屋外露出による塗膜の亀裂、剥離等が発生する等の物性的な脆弱点とプライマ層とフッ素層等２回以上塗装しなければならない生産性の低下をもたらす問題点があった。
【０００５】
このようにソリッドタイプ及びメタリックタイプの無機塗料の場合、金属素材の質感及び模様を期待できず、着色透明有機塗料の場合、物性低下で建築資材、各種素材の機能性表面塗装を期待し難い。
【０００６】
また、塗料組成物が基材に透明に処理した後、染色槽に数分乃至数十分沈漬させた後着色させる方法（大韓民国特許公開９１−３０５１、大韓民国特許公告８９−２８９２）がある。この方法は、プラスチックレンズの眼鏡を着色させる方法で紫外線遮断、基材保護等の効果が一時的にあるが、塗膜の耐熱性がなく、加熱時脱色が予想され、長期間屋外露出時に発生される染色色相の脱色と使用された有機紫外線吸収剤の燃焼による基材の損傷で塗膜の亀裂、剥離等が発生することから、建築用や熱機器等の用途として使用できなかった。
【０００７】
金属を鍍金及び着色処理する場合、例えばチタン・ステンレススチール・アルミニウム等の金属表面に自然発色、電解着色、科学着色等で金色及び各種有色処理方法があるが、この処理費用が相当な高値で色相の具現に限界があり、色が均等でない短所と共に最終的に表面保護層を再び塗装しなければならない問題点等で広範囲に活用され難い。それ以外に最近では、物理的蒸着法（ＰＶＤ、ＰｈｉｓｉｃａｌＶａｐｏｒＤｅｐｏｓｉｔｉｏｎ）としてスパッタリングによるＴｉＮ，ＴｉＣ等の被膜を表面に処理し着色効果を出す方法が登場したが、素材の大きさによる真空容器が必要になり、多用な色相には限界があり、価格及び表面保護層の形成、均等な色相の組成等に同様の問題点があった。
【０００８】
前記のような問題点を解決するため、即ち、場所及び大きさにとらわれない塗料タイプで色相調節が簡単で、低廉かつ広範囲に活用できる方法として無機塗料組成物の中から顔料及び充填剤を除外して、着色有機顔料または染料を使用する方法が研究されているが、この場合は着色透明有機塗料に比べ耐熱性の増加、硬度の向上、耐溶剤性の向上等大部分の物性が向上されるが、これもセラミック塗布組成物の中に有機染料が潜在するため、可視光線の選択吸収がなされる着色透明効果が２５０℃以上での脱色、紫外線調査による脱色で本来の目的である着色透明効果を消失し、有機顔料及び染料の人体に有害な毒性物質及び環境ホルモン等の湧出で建築資材や各種素材の機能性表面塗装を充足できない等いろいろな問題点があった。
【０００９】
【発明が解決しようとする課題】
本発明は前記のような問題点を鑑みてなされたもので、その目的はステンレススチール合金・チタン金属・アルミニウム及びアルミニウム合金等の金属と、車両用強化ガラス・建築物窓ガラス・各種金属蒸着ガラス等のガラス、プラスチック、紙等の表面にコーティング、硬化し美麗な美装性、透明性、耐候性、耐熱性、耐汚染性、高硬度、耐水性、密着性、耐蝕性、耐久性、遠赤外線放射性等が優れた建築用内外装材及び台所機器用塗膜を形成できる着色透明無機塗料組成物とその製造方法及び組成物コーティング方法を提供することである。
【００１０】
【課題を解決するための手段】
本発明は、０．７〜４１．７重量％の有機アルコキシシランの加水分解物及び縮合物と、水及び／又はアルコールを分散媒体にする粒子の大きさが平均５〜１００ｎｍであり、ｐＨ２〜１０である、固形分に換算して０．２７〜１８．６重量％のコロイドジルコニアと、水及び／又はアルコールを分散媒体にする粒子の大きさが平均５〜１００ｎｍであり、ｐＨ２〜１０である、固形分に換算して０．０２〜３．８重量％のコロイドアルミナと、水及び／又はアルコールを分散媒体にする粒子の大きさが平均５〜３００ｎｍであり、固形分に換算して０．０２〜２７．９重量％のコロイド無機顔料と、加水分解触媒に使用される０．０１〜３重量％の酸とを含む着色透明無機塗料組成物であって、前記コロイドジルコニア、前記コロイドアルミナ、及び前記コロイド無機顔料の少なくとも一つは、水を含み、前記着色透明無機塗料組成物に含まれる水の重量百分率は、０．６〜４５．４重量％であり、前記着色透明無機塗料組成物に含まれるアルコールの重量百分率は、１５．９〜９５．４重量％である着色透明無機塗料組成物とその製造方法及び組成物コーティング方法を提供する。
【００１１】
【発明の実施の形態】
図１はチタン鋼板（表面バイブレーション前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）を、図２はステンレス鋼板（表面ヘアライン前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）を、図３は無色透明ガラス瓶（脱脂前処理）に着色透明組成物コーティング処理前後の写真（上段は処理前、下端は処理後）を、図４は装飾カップ（表面アルミニウム模様蒸着前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）を、図５はステンレス鍋（表面光沢研磨、脱脂前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）を、図６はステンレス鍋の着色透明組成物コーティング処理前後の変色促進試験の結果グラフを、図７は紙ベーキングカップに着色透明組成物コーティング処理前後のベーキング写真（左側は両面処理、中央は内面処理、右側は未処理）を、図８は紙ベーキングカップの温度別遠赤外線放射量（Ｗ／ｃｍ^２）測定比較の結果グラフを示し、本発明は有機アルコキシシランにアルコール系コロイドを入れて攪拌及び混合しａ液を製造して、水系コロイドに水と酸触媒を入れて攪拌及び混合しｂ液を製造した後、前記ｂ液を攪拌しながらａ液に滴下・反応して、反応終了後約３０〜９０分間攪拌を維持してコーティング方法にしたがい不揮発分組成をするためアルコールを入れた後密封し常温で１〜２４時間熟成する。
【００１２】
即ち、本発明は前記の過程を通して０．７〜４１．７重量％の有機アルコキシシランの加水分解物及び縮合物と、水またはアルコールを分散媒体にする粒子の大きさが平均５〜１００ｎｍであり、固形分に換算して０．２７〜１８．６重量％のコロイドジルコニアと、水またはアルコールを分散媒体にする粒子の大きさが平均５〜１００ｎｍであり、固形分に換算して０．０２〜３．８重量％のコロイドアルミナと、水またはアルコールを分散媒体にする粒子の大きさが平均５〜３００ｎｍであり、固形分に換算して０．０２〜２７．９重量％のコロイド無機顔料と、前記水を分散媒体にしたコロイドジルコニア・コロイドアルミナ・コロイド無機顔料に含有された０．６〜４５．４重量％の水と、前記有機アルコキシシランに含有されたアルコールと前記アルコールを分散媒体にしたコロイドジルコニア・コロイドアルミナ・コロイド無機顔料に含有された１５．９〜９５．４重量％の低級脂肪族アルコールと、０．０１〜３重量％の加水分解触媒に使用される酸とを含んでなる着色透明無機塗料組成物とその製造方法及び各種基材（金属、プラスチック、セラミック等）表面を前処理する方法、製造された着色透明無機塗料組成物の塗布方法、硬化方法を含んだコーティング方法を含む。
【００１３】
前記有機アルコキシシランは、一般式ＲＳｉ（ＯＲ’）_３（Ｒは炭素数１〜８の有機基、Ｒ’は炭素数１〜５のアルキル基または炭素数１〜４のアシル基を示す）に代表されるもので、加水分解し生成された加水分解及び部分縮合物が使用される。前記有機アルコキシシランの加水分解物と部分縮合物は有機アルコキシシランを加水分解させて得られる。有機アルコキシシランは水と酸触媒として加水分解反応が生じ加水分解物を生成し、連続的に重縮合反応が生じ部分縮合物が得られる。
【００１４】
ここで、ＲＳｉ（ＯＲ’）_３で示される有機アルコキシシランのＲは炭素数１〜８の炭素を有する有機基として、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基等のアルキル基、それ以外のγ−クロロプロピル基、ビニル基、３，３，３−トリフルオロプロピル基、γ−グリシドプロピル基、γ−メタクリロキシプロピル基、γ−メルカプトプロピル基、フェニル基、２−（３，４−エポキシシクロヘキシル）エチル基、γ−アミノプロピル基等である。
【００１５】
またＲ’は炭素数１〜５のアルキル基または炭素数１〜４のアシル基として、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、アセチル基等である。
【００１６】
このような有機アルコキシシランの具体的な例として、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリエトキシシラン、ｉ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−クロロプロピルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３，３，３−トリフルオロプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、フェニルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等があげられ、有機アルコキシシランは１種または２種以上を併用し使用する。
【００１７】
ここでの有機アルコキシシランは、特にメチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシランが望ましい。有機アルコキシシランの加水分解で作られた部分縮合物は組成物の中で有機アルコキシシランに水を加え生成されるもので別途に加水分解させて得るものよりもよい。この加水分解縮合物はビヒクルとして結合剤の役割をする。
【００１８】
前記有機アルコキシシランの組成物の中で配合は加水分解及び部分縮合物に換算し０．７〜４１．７重量％で、望ましくは４．６〜１８．４重量％として０．７重量％未満で得られた塗膜は密着性が悪く、満足できる硬度等物性が得られず、４１．７重量％を超える場合塗膜の亀裂及び剥離が発生しやすく、組成物の保存安定性が悪いため避けるほうがよい。
【００１９】
前記水又は／及び有機溶媒を分散媒体にしたｐＨ２〜１０のコロイドジルコニアはコロイドシリカに比べて耐熱及び接着性に優れ、特にジルコニア固有の耐熱衝撃特性及び被膜の硬度向上と優秀な接着力の特性を付与するためのもので、本発明品の核心原料である。コロイドジルコニアの粒子の大きさは５〜１００ｎｍで、５〜８０ｎｍが良好で、コロイドジルコニアの配合量は固形分に換算し０．２７〜１８．６重量％で、望ましくは１．４〜５．６重量％である。前記コロイドジルコニアの配合量が固形分に換算し０．２７重量％未満の場合、接着力及び硬度が低下されて、塗膜の亀裂が発生し得、１８．６重量％超過時には薄黄色をおびた透明性の特性が低下する現象が生じ得る。
【００２０】
前記水又は／及び有機溶媒を分散媒体にしたｐＨ２〜１０のコロイドアルミナはアルミナの優れた硬度及び耐磨耗の特性を付与するため添加し、コロイドアルミナの粘度変化の特性による塗料組成物の粘度向上と表面の陽電荷分布による塗料の安定化の目的としても使用する。アルミナの粒径は平均５〜１００ｎｍが良好で、配合量は固形分に換算し０．０２〜３．８重量％で、望ましくは０．２〜０．８重量％である。前記コロイドアルミナの配合量が固形分に換算し０．０２重量％未満の場合、硬度及び耐磨耗性の特性が低下されて、３．８重量％超過時には粘度の急上昇により塗料の凝集が発生される。
【００２１】
前記水又は／及び有機溶媒を分散媒体にしたコロイド無機顔料は、ｐＨ２〜１０の酸化物、窒化物、硫化物、カドミウム化物等の１種または２種以上の化合物として、単独酸化物としてはＴｉＯ_２（酸化チタン、鋭錐石、ルチル）、ＺｎＯ（酸化亜鉛、亜鉛化）、ＣｏＯ（酸化コバルト）、Ｃｒ_２Ｏ _３（酸化クロム）、Ｆｅ_３Ｏ _４（フェライト）、Ｆｅ_２Ｏ _３、ＦｅＯ（酸化第一鉄、酸化第二鉄）、ＣｕＯ（酸化銅）等の遷移金属単一酸化物、（Ｃｕ・Ｃｒ）酸化物、（Ｔｉ・Ｃｏ）酸化物、（Ｔ・Ｎｉ）酸化物、（Ａｌ・Ｃｏ）酸化物、（Ｃｏ・Ｐ）酸化物、（Ｃｒ・Ａｌ）酸化物、（Ｃｒ・Ｓｎ）酸化物、（Ｆｅ・Ｚｒ）酸化物、（Ｆｅ・Ｚｎ）酸化物、（Ｆｅ・Ｃｒ・Ｚｎ）酸化物、（Ｆｅ・Ｃｏ・Ｃｒ）酸化物、（Ｃｏ・Ｃｒ・Ａｌ）酸化物、（Ｔｉ・Ｆｅ・Ｚｎ）酸化物、（Ｃｒ・Ｃｕ・Ｍｎ）酸化物、（Ｔｉ・Ｎｉ・Ｃｏ）酸化物、（Ｆｅ・Ｃｒ・Ａｌ・Ｚｎ）酸化物、（Ｔｉ・Ｎｉ・Ｃｏ・Ａｌ）酸化物等の２〜４種の複合酸化物と、窒化物としてはＴｉ窒化物、Ｚｒ窒化物等の単独窒化物、（Ｔｉ・Ａｌ）窒化物、（Ｔｉ・Ａｌ・Ｃ）窒化物等の２〜３種の複合窒化物、硫化物としては（Ｃｄ・Ｚｎ）硫化物、カドミウム化物としては（Ｓ・Ｓｅ）カドミウム化物があり、これをピグメント番号で区分すると、ブラック２６、ブラック１１、ホワイト、レッド１０８、レッド１０１、オレンジ２０、イエロー１８４、イエロー３５、グリーン２６、コバルトブルー２８、バイオレット１６等に区分する。コロイド状無機顔料の製造は、無機顔料を水または有機溶媒を媒質として超微分粉砕器を使用し超微粒子粉砕・製造し、この他にもゾルゲル法、パイロゾル法等でも製造し、最終的にコロイドの安定化のためにｐＨ調節、固形分調節、有機表面改質等でコロイド無機顔料を完成する。水又は／及び有機溶媒を分散媒体にしたコロイド無機顔料の粒径は平均５〜３００ｎｍで、望ましくは５〜１００ｎｍの範囲である。
【００２２】
本発明品の着色透明性を示すのに使用するコロイド無機顔料は不揮発分に換算し０．０２〜２７．９重量％を使用し、望ましくは３．８〜１５重量％である。前記コロイド無機顔料の配合量が固形分に換算し０．０２重量％未満の場合、着色効果、紫外線遮断、電磁波吸収効果がなく、２７．９重量％超過時には塗膜の色不均等、不透明化、塗料の凝集が発生される。
【００２３】
前記組成物中の水は、水を分散媒体としたコロイドジルコニア、コロイドアルミナ、コロイド無機顔料の使用される水を含み０．６〜４５．４重量％で、より望ましくは５．３〜２１重量％である。前記コロイドジルコニア、コロイドアルミナ、コロイド無機顔料の分散媒体に使用される水は、酸触媒と共に有機アルコキシシランと加水分解反応をおこす。水の量が０．６重量％未満の場合は、加水分解反応が生じにくく、４５．４重量％を超過する場合は、光沢及び製膜性が低下されて、水の蒸発遅延による塗膜のピンホール発生、耐薬品性が低下する。使用される水は、純粋に近い蒸留水以外にも、浄化水、水道水等も塗膜の悪影響を与えない純度でなら使用してもよい。
【００２４】
前記脂肪族アルコール類は、有機アルコキシシランを溶解させ組成物を安定化させて、系内に存在する余剰水分を共沸留去させた時に有機アルコキシシランの縮合を抑制するため添加される。また、塗膜の硬化時、塗膜のレベリング性、周辺湿度による調節能力等を提供する。前記アルコールには、メタノール、エタノール、プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール等があり、これを１種または２種以上を使用する。本発明で使用するアルコールは、有機アルコキシシラン、コロイドジルコニア、コロイドアルミナ、コロイド無機顔料に含有されたアルコールを含み１５．９〜９５．４重量％を使用し、より望ましくは３４．８〜７６．５重量％の範囲である。脂肪族アルコールの量が１５．９重量％未満の場合、製造時の反応が生じにくかったり急激な反応が生じ、塗料の固形分の過多による塗膜の厚さの調節混乱及び塗料の安定性が低下し、９５．４重量％超過する場合は、粘度と隠蔽力が低下して、反応が生じにくく、非常に低い不揮発分により塗膜として認められず、塗布及び塗布セッティング時に、溶剤の気化潜熱により湿気を吸収し塗膜の透明性が低下する。
【００２５】
前記無機酸または／及び有機酸は、有機アルコキシシランの加水分解時に加水分解触媒として使用するもので、０．０１〜３重量％添加する。酸としては塩酸、硫酸、硝酸、リン酸、蟻酸、酢酸、安息香酸、ｐ−トルエンスルホン酸、クエン酸等を使用する。本組成物の加水分解に使用される無機酸及び有機酸は、１種単独あるいは２種以上を併用しｐＨを２〜７にする。酸の濃度が高いと反応速度が急激に上昇して、激烈な発熱反応及び簡単にゲル化される等の問題点がある。その反対に、低すぎると反応が簡単におこらず、低温では反応熱なく簡単にゲル化が発生する等の問題がある。
【００２６】
本発明を実施例により詳細に説明する。
（実施例１）
［試験素材／表面前処理］
本発明で適用される素材は、チタン鋼、ステンレス鋼、アルミニウム及びアルミニウム合金等の金属類、ガラス、タイル等のセラミック類、ポリカボネート、アクリル、ＰＥＴ等のプラスチック類、紙等がある。
【００２７】
また、素材の前処理は、物理的方法、化学的方法及びプライマー等の方法に区分できる。物理的方法は、サンドブラスト、ショートブラスト、ドライアイスブラスト、ヘアライン、バイブレーション等がある。化学的方法は、アルミニウム蒸着、陽極酸化皮膜、電解着色と全ての試験で最終洗浄するアルカリ脱脂等がある。プライマー処理は、プラスチックのような無機質塗料との接着が不可能な場合に使用し、熱機器や各種装飾及び標識を目的とするシルクスクリーン印刷を下塗りで使用する。
【００２８】
表１は、素材別前処理方法及び区分を示し、本発明に使用された素材及び前処理方法ａ１〜ｊ３で本発明品の素材の種類及び前処理方法は限定されない。
［塗料組成／製造］
本発明の塗料組成物に関する具体的な配合例は、表２乃至表４の塗料組成物、Ａ〜Ｒに示した。本発明の塗料組成の一般的な製造／合成方法は次の通りである。
［混合液Ａ製造］
有機アルコキシシランとアルコールを分散媒体とするコロイドジルコニア又は／及びコロイドアルミナまたは／及びコロイド無機顔料を混合し、約０．５リットルの容器に入れて、約５００〜８００ｒｐｍの速度で攪拌しながら５±３℃で維持させて、あるいは混合液から出る反応を抑制／維持し混合液Ａを製造する。
［混合液Ｂ液製造］
一方、他の１．５リットルの反応容器に水を分散媒体にするコロイドジルコニア又は／及びコロイドアルミナ又は／及びコロイド無機顔料、余分の水を入れて約５００〜８００ｒｐｍの速度で攪拌しながら反応触媒に酸（無機酸又は／及び有機酸）を添加しｐＨ＝２〜７にして、混合液の発熱反応によるコロイド粒子の凝集をふせぐため攪拌液の温度は１０±５℃で維持させて混合液Ｂを製造する。
［混合液Ａ＋Ｂ製造］
製造した混合液Ｂを約５００〜８００ｒｐｍの速度で攪拌して、攪拌液の温度は２５±５℃に維持させ先に製造した混合液Ａを１分当たり５〜２０ｃｃ程度で発熱反応温度を２５±５℃になるよう調節しながら滴下する。混合液Ａの滴下が終了した後約３０〜９０分攪拌を維持してコーティング方法にしたがい不揮発分調整をするためアルコールを入れた後密封し常温（２５℃）で１時間〜４時間熟成し着色透明無機塗料組成物を製造する。また、前記塗料組成物の中でプラスチックに適用する塗料組成物（Ｐ及びＱ）の場合には低温硬化を促進するためリチウムアセテートと蟻酸とを２：３の比率（重量比）で混合溶解した溶液をＰ及びＱの不揮発分に対し３〜５重量％添加する。
【００２９】
本発明に使用された組成例Ａ〜Ｒで本発明品の着色透明無機塗料組成物を限定せず、また前記Ａ、Ｂ液の製造方法も実施例により限定されるものではない。即ち、有機アルコキシシランとアルコールを分散媒体にするコロイド無機顔料を攪拌・混合し混合液Ａを製造して、水を分散媒体にするコロイドジルコニア及びコロイドアルミナに水と反応触媒に酸（無機酸又は／及び有機酸）を添加した後攪拌・混合し混合液Ｂを製造してもよく、最終的には塗料組成物が０．７〜４１．７重量％の有機アルコキシシランの加水分解物及び縮合物と、水又はアルコールを分散媒体にする粒子の大きさが平均５〜１００ｎｍであり、固形分に換算し０．２７〜１８．６重量％のコロイドジルコニアと、水又はアルコールを分散媒体にする粒子の大きさが平均５〜１００ｎｍであり、固形分に換算し０．０２〜３．８重量％のコロイドアルミナと、水又はアルコールを分散媒体にする粒子の大きさが平均５〜３００ｎｍであり、固形分に換算し０．０２〜２７．９重量％のコロイド無機顔料と、前記水を分散媒体にしたコロイドジルコニア・コロイドアルミナ・コロイド無機顔料に含有された０．６〜４５．４重量％の水と、前記有機アルコキシシランに含有されたアルコールと前記アルコールを分散媒体にしたコロイドジルコニア・コロイドアルミナ・コロイド無機顔料に含有された１５．９〜９５．４重量％の低級脂肪族アルコールと、０．０１〜３重量％の加水分解触媒に使用される酸とからなる製造方法を含む。
［コーティング方法及び硬化方法］
本発明に使用するコーティング方法は、一般スプレーコーティング、静電コーティング、ディップコーティング、ロールコーティング（バーコーティングを含む）、フローコーティング、筆塗り等全て可能である。本発明に使用する硬化方法は、コンベア式又はベルトタイプのＬＰＧ、石油、電気方式の加熱方式の連続オーブン、配置タイプのボックスオーブン、メカニカルコンベクションオーブン、恒温恒湿槽等最高１８０℃まで昇温可能な加熱方式ならば全て可能である。コーティング方法及び硬化方法の具体的な例は表５に示す。本実施例に使用されたコーティング方法及び硬化方法Ｚ−１〜Ｚ−１０でコーティング方法及び硬化方法を限定しない。
［塗膜の外観及び物性試験結果］
表１の試験素材及び表面前処理による素材準備と表２乃至表４の塗料組成物による塗料の準備、また表５のコーティング方法及び硬化方法による塗膜を形成し表６及び表７に、これにともなう塗膜の外観評価を示す。
【００３０】
表８及び表９に、本発明品の試験方法を示し、この試験方法による本発明品の塗膜の総合物性を表１０乃至表１７に示す。塗膜の総合物性表結果の中で記号“０”は“異常なし”
又は“汚染なし”を示す。
【００３１】
【表１】

＊（１）日本、日鉄（株）製品、チタン鋼板
＊（２）日本、日鉄（株）製品、ステンレス鋼板、ＳＵＳ−３０４
＊（３）３ｍｍ：韓国、大韓アルミニウム（株）製品、アルミニウム合金鋼板、Ａ３００３
１５μｍ：韓国三亜アルミニウム（株）製品、クッキングホイル
＊（４）韓国、斗山包装（株）製品、フルーツジュースの容器、透明（無着色ガラス）
＊（５）韓国、韓国ガラス（株）製品、市販の板ガラス
＊（６）韓国、大宝窯業（株）製品、市販の白色タイル
＊（７）米国、ゼネラルエレクトリック（株）製品、Ｌｅｘａｎ
＊（８）韓国、ＬＧ化学（株）製品
＊（９）韓国、三養社（株）製品
＊（１０）紙ファン／カップ：韓国慶一包装（株）製品、パウンドカップ、ベーキングファン
パルプモールド：韓国リサイト（株）製品
＊（１１）サンドブラスト器を使用、サンディング砂：１００ｍｅｓｈ、サンディング粗度：２〜３μｍ
＊（１２）ショートブラスト器を使用、ショートボール：０．５ｍｍステンレススチールボール、ショート粗度：１〜２μｍ
＊（１３）ドライアイスブラスト（日本、日本酸素（株）製品、マジックブラスト）使用、ショート剤：ドライアイスペレット
＊（１４）ステンレス鋼板表面の研磨剤の連続研磨方法によるヘアライン加工
＊（１５）金属鋼板表面のバイブレーション研磨処理による表面加工
＊（１６）韓国、アイメックス（株）製品、アルミニウム真空蒸着したガラスのカップ（模様蒸着）、ガラス断面蒸着
＊（１７）アルミニウム合金、Ａ３００３、陽極酸化処理、アルマイト皮膜の厚さ：１２μｍ、封空未処理
＊（１８）ステンレス鋼、チタン鋼の化学的処理による電解着色（ブラック、ブロンズ、ブルー、ゴールド、レッド、グリーン等５色相）、薬液による浮動態処理皮膜で皮膜の厚さは約０．０００２〜０．２５μｍ
＊（１９）韓国、南邦化工（株）製品、ナバケムＮＢ−１に沈積又は擦って洗浄した後５℃の蒸留水で残留脱脂液除去、乾燥
＊（２０）日本、東芝シリコン（株）製品、プライマーＰＨ−９１（アクリル，ＰＥＴ用）、ＰＨ−９３（ポリカボネート用）にスプレー／ディッピング塗布後３０〜４０℃で１０分乾燥
＊（２１）韓国、大韓ファインセラミック（株）製品、セラインクＣＩ−３００でシルクスクリーン（♯２５０）印刷後常温又は／及び３０〜４０℃で２０分以上乾燥
【００３２】
【表２】

＊＊（１）日本、東芝シリコン（株）、日本、信越（株）製品
＊＊（２）日本、日産化学（株）、米国、ニャコール（株）、米国、ナノフェイス（株）製品、日本、富士顔料（株）
＊＊（３）日本、日産化学（株）、米国、ニャコール（株）、米国、ナノフェイス（株）、ドイツ、テグサ（株）製品
＊＊（４）日本、日産化学（株）、米国、ニャコール（株）、米国、ナノフェイス（株）、日本、富士顔料（株）製品
【００３３】
【表３】

【００３４】
【表４】

【００３５】
【表５】

＊＊＊（１）一般のエアースプレー（Ｗ−６１、日本、岩田（株）製品等）使用
＊＊＊（２）日本、ランスバーグインダストリ（株）製品、インバータレシプロケータ（ＩｎｖｅｒｔｅｒＲｅｃｉｐｒｏｃａｔｏｒ）とマイクロベル９６を使用する高電圧静電スプレー装置を次のセッティング条件で使用する。
−吐出量：８０〜１１５ｃｃ／ｍｉｎ
−コンベア速度：１．５〜１．６ｍ／ｍｉｎ
−印加電圧：６０ｋＶ
−回転数：１７，０００〜２０，０００ｒｐｍ
−ストローク：６００ｍｍ
−ストローク速度：３０〜４０ｍ／ｍｉｎ
＊＊＊（３）プリングマシーン（ＰｕｌｌｉｎｇＭａｃｈｉｎｅ）を使用しコーティング剤に漬けておいた試験試片を一定の速度で引き上げコーティングする方法
＊＊＊（４）ロールコーティングで実験的にはバーコーター（ＢａｒＣｏａｔｅｒ）を使用し、“バーコーター番号×３／２＝湿潤塗膜の厚さ”で計算
【００３６】
【表６】

＊＊＊＊（１）ＵＶ−ＶＩＳ分光計、可視光線領域の分光透過率
【００３７】
【表７】

【００３８】
【表８】

＊＊＊＊＊（１）ＫＳ、ＪＩＳ、ＡＳＴＭは各々韓国、日本、米国の工業規格
＊＊＊＊＊（２）米国建築製作者協会（ＡｍｅｒｉｃａｎＡｃｈｉｔｅｃｔｕｒａｌＭａｎｕｆａｃｔｕｒｅｒＡｓｓｏｃｉａｔｉｏｎ）塗膜試験方法
【００３９】
【表９】

【００４０】
【表１０】

【００４１】
【表１１】

【００４２】
【表１２】

【００４３】
【表１３】

【００４４】
【表１４】

【００４５】
【表１５】

【００４６】
【表１６】

【００４７】
【表１７】

【００４８】
【表１８】

＊＊＊＊＊＊（１）耐紫外線性：紫外線ランプ（日本、東芝（株）製品、ブラックライト４ＷＦＬ４ＢＬ−Ｂ）を垂直５ｃｍの距離にガラスのカップを置いて１２８時間調査）
【００４９】
【表１９】

＊＊＊＊＊＊＊（１）変色促進試験：６０℃１０％の硝酸溶液に１０日間沈積し変色の有無を確認
【００５０】
【表２０】

＊＊＊＊＊＊＊＊（１）パウンドカップを水に沈積／１時間後紙の水からのめくれの可否評価
＊＊＊＊＊＊＊＊（２）ヒ素（限度内）、重金属（１０ｐｐｍ以下）、ホルムアルデヒド（限度内）、蛍光増白剤（不検出）、タル色素（不検出）、蒸発残留量（３０ｍｇ／ｌ以下）
＊＊＊＊＊＊＊＊（３）ベーカリー用オーブン（２００〜３００℃）にケーキを焼く時の紙のパウンドカップの変色の可否及びオーブン使用の可能性の可否
［実施例２］
無色透明ガラスカップにアルミニウム蒸着模様を作った後アルカリ脱脂をして、装飾ガラスカップ（韓国アイメックス（株）製品）前処理を完了（表１の試験素材及び表面前処理による素材準備の中で試片番号ｄ３と同様の前処理）する。着色透明無機塗料組成物は、表３のＧ組成にし、市販のアクリル焼付樹脂にジャポン染料（ドイツ、パスフ（株）製品、ジャポンオレンジ２４４）を添加して作った着色透明塗料にする。前記組成物及び比較例のコーティング及び硬化方法は表５のＺ−３の工程で行って、図２に着色透明無機塗料組成物の処理前及び処理後の写真を示し、前記組成物及び比較例の塗膜の外観及び塗膜の物性の試験結果は表１８に示す。塗膜の物性結果の中で記号“０”は“異常なし”又は“変色なし”を示し、“×”は“不良”又は“脱色”を示す。
［実施例３］
ステンレス鋼板材質の台所容器（韓国、アルドマジョン（ＡＲＴＤＥＭＡＪＯＮ）（株）製品、大きさ：直径３０ｃｍ×深さ２０ｃｍ）表面を光沢研磨した後、アルカリ脱脂しステンレス台所容器前処理を完了（表１の試験素材及び表面前処理による素材準備の中で試片番号ｂ１と同様の前処理）する。着色透明無機塗料組成物は表３のＧ組成にし、コーティング及び硬化方法は表５のＺ−３の工程で実行する。比較ではステンレス表面光沢研磨された市販製品を使用する。図５に着色透明無機塗料組成物の処理前及び処理後の写真を示し、塗膜の外観及び塗膜の物性試験結果は表１９に示し、図６は変色促進試験結果を示した。塗膜物性結果の中で記号“０”は“異常なし”又は“変色なし”を示し、“×”は“変色”を示す。
［実施例４］
紙のパウンドカップ（韓国慶一（株）製品、パウンドカップ）を準備し着色透明無機塗料組成物の表３の０組成にし、コーティング及び硬化方法は表５のＺ−２の工程で着色透明無機塗料が塗布された紙のパウンドカップ２種類（カップの内外部を塗布する両面処理とカップの内部のみ塗布する内面処理）を作り、比較例には市販されている未処理の紙のパウンドカップを準備する。本発明品が処理されたパウンドカップと未処理のパウンドカップにケーキの生地を入れ２００〜２５０℃のオーブンで約２０分間焼いた後他の物性評価と共に比較（図７参照）する。塗膜の外観及び塗膜の物性の試験結果は表２０に示し、遠赤外線放射比較グラフは図８に示した。塗膜の物性結果の中で記号“０”は“異常なし”又は“良好”を示し、“×”は“浸る”又は“不良”を示す。
【００５１】
本発明は、上述した特定の望ましい実施例に限定されず、請求範囲で請求する本発明の要旨から脱落せず、当該発明が属する技術分野で通常の知識をもつ者なら誰でも多様な変形実施が可能なことはもちろん、その変形は請求範囲に記載の範囲内である。
【００５２】
【発明の効果】
本発明は、コロイド無機顔料を使用し塗膜の着色透明効果と共に高い熱及び紫外線に長期間露出しても変色や脱色がなく安定して、金属表面の質感をそのまま保ったまま着色透明効果と金属表面の保護を同時に付与することで鍍金、電解着色、スパッタリングのような方法から表れる問題点、即ち、大きさの制限、排水汚染、色相不均等等がなく、金属表面保護のための２次的作業を省くことができる。
【００５３】
即ち、金属、プラスチック、ガラス、紙等の基材表面に機能性着色機能を付与する本発明、着色透明無機塗料組成物のコーティングにより形成された塗膜は、可視光線と紫外線の一部波長を除外し、大部分が透明で黒色、白色、赤色、黄色、緑色、青色、紫色に至るまで多様な着色透明効果が得られる。
【００５４】
また、本発明を金属基材類、ガラス類、紙等表面にコーティング、硬化する場合、有機着色顔料等を添加した着色塗料や染色タイプに比べて美麗な美装性、耐候性、耐汚染性、高硬度、耐水性、密着性、耐蝕性、耐久性等が非常に優れている。
【００５５】
このような機能的特性で建築用内外装剤、熱機器等産業全般にわたり広範囲な用途の塗膜を形成し、限定的な素材で広範囲で機能的な新素材として代替されると期待できる。
【００５６】
また、本発明に使用したコロイド無機顔料と酸化物の特性即ち、可視光線以外の紫外線吸収、遠赤外線の放出、電磁波の吸収の特性を各種基材に適用できる。
【００５７】
本発明をプラスチック基材表面に適用する場合、紫外線が基材表面に到達するのを完全に遮断して、表面硬度も向上され基材及び基材裏面の物品を紫外線及び外部環境から保護する。
【００５８】
本発明をアルミニウムクッキングホイル及び紙類に適用する場合、高い遠赤外線放射効果と非粘着性の特性が得られ、電子レンジでも使用可能な加熱容器に使用できる。
【００５９】
既存のソリッドカラー、メタリックカラーに依存していた建築用内・外装材の分野及び産業用応用分野に透明カラー、即ち第３のカラーの本格的な具現が可能になることにより、即ち、ソリッドカラーとメタリックカラーを本発明の着色透明組成物の着色透明カラーと組合わせると想像もできないほどの甚だしい色相の具現が可能になることから国旗建築及び産業デザインと国旗の色彩具現の技術力に大きな影響を及ぼすと予想される。
【００６０】
この他にも、本発明の組成物の無機塗料の物性以外にも光学的な特性、即ち、着色透明無機顔料の固有波長の吸収及び放出の特性を利用した紫外線遮断、遠赤外線放出又は熱線反射、電磁波吸収機能が付与されることにより透明かつ有害な紫外線遮断、熱線反射／放出、電磁波遮断／吸収、透明資材／機能材料を表面コーティング処理だけでも簡単に採用できる等多くの効果がある。
【図面の簡単な説明】
【図１】本発明のチタン鋼板（表面バイブレーション前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）である。
【図２】本発明のステンレス鋼板（表面ヘアライン前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）である。
【図３】本発明の無色透明ガラス瓶（脱脂前処理）に着色透明組成物コーティング処理前後の写真（上段は処理前、下段は処理後）である。
【図４】本発明の装飾カップ（表面アルミニウム模様蒸着前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）である。
【図５】本発明のステンレス鍋（表面光沢研磨、脱脂前処理）に着色透明組成物コーティング処理前後の写真（左側は処理前、右側は処理後）である。
【図６】本発明のステンレス鍋の着色透明組成物コーティング処理前後の変色促進試験結果図である。
【図７】本発明の紙ベーキングカップに着色透明組成物コーティング処理前後のベーキング写真（左側は両面処理、中央は内面処理、右側は未処理）である。
【図８】紙ベーキングカップの温度別遠赤外線放射量（Ｗ／ｃｍ^２）測定比較結果図である。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a colored transparent inorganic coating composition, a method for producing the same, and a method for coating the composition, and a colored transparent inorganic coating composition for imparting a functional coloring function to the surface of a substrate such as metal, plastic, glass, paper, and the like. The present invention relates to a method and a composition coating method.
[0002]
[Prior art]
In general, the surface of products such as cement, glass, plastic, paper, etc., such as stainless steel and aluminum, and inorganic paints are coated and cured, beautiful appearance, heat resistance, weather resistance, contamination resistance, high hardness, Functional paints that impart water resistance, adhesion, far-infrared radiation, corrosion resistance, durability, cold resistance, and the like have been applied to various fields.
[0003]
Colored inorganic paints (Korea Patent Publication 95-18360, Korea Patent Publication 97-42865, Korea Patent Application 98-31088, Japan Patent Publication Sho 53-5042, Japan Patent Publication Sho 63-75073, Japanese Patent Publication Sho 63- 81176, Japanese Patent Publication No. 1-149866), a coating composition such as a solid type based on white, black and three primary colors and a metallic type which imparts a metallic hue is applied to the heat resistance of the coating film. Introducing the weather resistance and durability paint and coating method. In the case of the solid type and metallic type inorganic paints, it is an opaque paint that cannot directly express the texture and pattern of the material to be applied, for example, titanium, stainless steel, and aluminum.
[0004]
As the organic paint, there is an organic transparent colored paint using a colored transparent dye or the like. This shows the characteristics of organic paints such as thermal discoloration, low hardness, low weather resistance, dissolution by organic solvents, etc., and low physical properties such as the generation of toxic gases in the event of fire. Not suitable for surface coating. In the case of fluorine paint, weather resistance is superior to other organic paints, but its own bond strength depends on covalent bond, so it has poor adhesion to metal material and is applied to metal. Most use epoxy or acrylic primers. However, for building materials that require weather resistance, even if a transparent primer is used and a colored transparent fluorine paint is applied to a metal material such as titanium, stainless steel, or aluminum, the fluorine transparent coating layer is large. 100% of the part passes through the ultraviolet (UV) of sunlight, destroys the primer organic polymer and CO₂Decomposed into organic substances such as esters, the coating film of fluorine paint is extruded, and finally discoloration and peeling of the coating film occur. Of course, UV absorbers have been added to fluorine paints to solve the above-mentioned problems, but UV absorbers are also decomposed by UV rays, so long-term weather resistance can be achieved with only a slight delay effect. It must be painted at least twice, including the physical weaknesses that cannot be compensated for, such as toxicity that may occur in the event of a fire, cracking or peeling of the coating film due to long-term outdoor exposure, and the primer layer and fluorine layer. There was a problem that caused a decrease in productivity.
[0005]
As described above, in the case of solid type and metallic type inorganic paints, the texture and pattern of metal materials cannot be expected, and in the case of colored transparent organic paints, it is difficult to expect functional surface coating of building materials and various materials due to deterioration of physical properties.
[0006]
In addition, there is a method (Korean Patent Publication No. 91-3092, Korean Patent Publication No. 89-2892) in which a coating composition is transparently treated on a base material and then immersed in a dyeing tank for several minutes to several tens of minutes before being colored. This method is a method of coloring glasses with plastic lenses, and has effects such as UV blocking and substrate protection temporarily, but there is no heat resistance of the coating film, decolorization is expected during heating, and it occurs when exposed outdoors for a long time Decoloration of the dyed hue and burning of the used organic ultraviolet absorber cause damage to the substrate, resulting in cracks, peeling, etc. of the coating film, so that it could not be used for architectural or thermal equipment.
[0007]
When metal is plated and colored, for example, there are gold and various colored treatment methods for natural coloring, electrolytic coloring, scientific coloring, etc. on the surface of metals such as titanium, stainless steel, and aluminum. However, it is difficult to make widespread use because of the problem that the surface protective layer must be repainted together with the disadvantages of uneven color. In addition, recently, as a physical vapor deposition method (PVD, Physical Vapor Deposition), a method of producing a coloring effect by treating the surface with a coating of TiN, TiC, etc. by sputtering has appeared, but a vacuum container is required depending on the size of the material Therefore, there are limits to the various hues, and there are similar problems in price, formation of a surface protective layer, composition of uniform hues, and the like.
[0008]
In order to solve the above problems, that is, a pigment type and a filler are excluded from the inorganic coating composition as a method that can be easily and inexpensively and widely used in a paint type that is not limited by location and size. However, methods using colored organic pigments or dyes have been studied. In this case, most of the physical properties such as increased heat resistance, improved hardness, and improved solvent resistance compared to colored transparent organic paints have been improved. However, since organic dyes are latent in the ceramic coating composition, the colored transparent effect that allows selective absorption of visible light is the original purpose of decolorization at 250 ° C. or higher, and decolorization by UV investigation. There were various problems such as the functional surface coating of building materials and various materials could not be satisfied due to the disappearance of the effects and the release of toxic substances and environmental hormones harmful to the human body of organic pigments and dyes.
[0009]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned problems, and its purpose is a metal such as stainless steel alloy, titanium metal, aluminum and aluminum alloy, tempered glass for vehicles, building window glass, and various metal-deposited glasses. Glass, plastic, paper, etc., such as coating, curing and beautiful appearance, transparency, weather resistance, heat resistance, stain resistance, high hardness, water resistance, adhesion, corrosion resistance, durability, distant An object of the present invention is to provide a colored transparent inorganic coating composition capable of forming an interior / exterior material for buildings and a coating film for kitchen appliances excellent in infrared radiation and the like, a production method thereof, and a composition coating method.
[0010]
[Means for Solving the Problems]
In the present invention, 0.7 to 41.7% by weight of the hydrolyzate and condensate of organoalkoxysilane and water and / or alcohol as a dispersion medium have an average particle size of 5 to 100 nm,pH 2-10.The average particle size of 5 to 100 nm in terms of solid content is 0.27 to 18.6% by weight of colloidal zirconia and water and / or alcohol as a dispersion medium,pH 2-10.The average particle size of the dispersion medium containing 0.02 to 3.8% by weight of colloidal alumina and water and / or alcohol in terms of solid content is 5 to 300 nm. A colored transparent inorganic coating composition comprising 02 to 27.9% by weight of a colloidal inorganic pigment and 0.01 to 3% by weight of an acid used for a hydrolysis catalyst, the colloidal zirconia, the colloidal alumina, And at least one of the colloidal inorganic pigments contains water, and the weight percentage of water contained in the colored transparent inorganic coating composition is 0.6 to 45.4% by weight, and the colored transparent inorganic coating composition Provides a colored transparent inorganic coating composition having a weight percentage of 15.9 to 95.4% by weight, a method for producing the same, and a method for coating the composition.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a photograph of a titanium steel plate (surface vibration pretreatment) before and after the colored transparent composition coating treatment (left is before treatment, right is after treatment), and FIG. 2 is a stainless steel plate (surface hairline pretreatment). Photo before and after coating treatment (left side before treatment, right side after treatment), Figure 3 before and after colored transparent composition coating treatment in a colorless transparent glass bottle (pre-degreasing treatment) (top is before treatment, bottom is after treatment) 4 is a photograph (before the treatment on the left side, after the treatment on the right side) before and after the colored transparent composition coating treatment on the decorative cup (surface aluminum pattern deposition pretreatment), and FIG. 5 is a stainless steel pan (before surface gloss polishing and degreasing) Processing) before and after the colored transparent composition coating treatment (left side before treatment, right side after treatment), FIG. Fig. 7 is a graph showing the results of the experiment, Fig. 7 is a baking photograph of the paper baking cup before and after the coating of the colored transparent composition (left side is double-sided processing, center is inner side processing, right side is untreated), and Fig. 8 is the temperature of the paper baking cup. Far-infrared radiation (W / cm²) Shows a graph of the results of measurement comparison. In the present invention, an alcoholic colloid is added to an organoalkoxysilane and stirred and mixed to produce solution a, and water and an acid catalyst are added to the aqueous colloid and stirred and mixed to prepare solution b. After the production, the solution b is dropped and reacted with the solution a while stirring. After completion of the reaction, stirring is maintained for about 30 to 90 minutes, and after adding alcohol to form a non-volatile composition according to the coating method, the solution is sealed. Aging for 1 to 24 hours at room temperature.
[0012]
That is, according to the present invention, 0.7 to 41.7% by weight of the hydrolyzate and condensate of organoalkoxysilane and water or alcohol as a dispersion medium are averagely 5 to 100 nm in size through the above process. The average particle size of the dispersion medium containing 0.27 to 18.6% by weight of colloidal zirconia and water or alcohol in terms of solid content is 5 to 100 nm, and 0.02 in terms of solid content. Colloidal inorganic pigment having an average particle size of 5 to 300 nm in water or alcohol as a dispersion medium and 0.02 to 27.9 wt% in terms of solid content. 0.6 to 45.4% by weight of water contained in colloidal zirconia, colloidal alumina, and colloidal inorganic pigment using water as a dispersion medium, and an alcohol contained in the organoalkoxysilane. 15.9 to 95.4% by weight of lower aliphatic alcohol and 0.01 to 3% by weight of hydrolysis catalyst contained in colloidal zirconia, colloidal alumina, and colloidal inorganic pigment using coal and alcohol as a dispersion medium. Colored transparent inorganic coating composition comprising acid used, method for producing the same, method for pretreating the surface of various substrates (metal, plastic, ceramic, etc.), and method for applying the produced colored transparent inorganic coating composition Coating methods including curing methods.
[0013]
The organoalkoxysilane has a general formula RSi (OR ')₃(R represents an organic group having 1 to 8 carbon atoms, R ′ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms), and hydrolysis produced by hydrolysis And partial condensates are used. The hydrolyzate and partial condensate of the organoalkoxysilane can be obtained by hydrolyzing the organoalkoxysilane. An organoalkoxysilane undergoes a hydrolysis reaction using water and an acid catalyst to produce a hydrolyzate, and a polycondensation reaction occurs continuously to obtain a partial condensate.
[0014]
Where RSi (OR ')₃R of the organic alkoxysilane represented by the formula is an organic group having 1 to 8 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or other γ-chloropropyl. Group, vinyl group,3, 3, 3-Trifluoropropyl group, γ-glycidpropyl group, γ-metacReRoxypropyl group, γ-meLeCaptopropyl group, phenyl group,2- (3,4-Epoxy cyclohexyl)An ethyl group, a γ-aminopropyl group, and the like;
[0015]
R ′ is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an acetyl group, and the like;
[0016]
Specific examples of such organic alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, and n-propyl. Triethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,3, 3, 3-Trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-metacReRoxypropyltrimethoxysilane, γ-meLeCaptopropyltrimethoxysilane, phenyltrimethoxysilane, γ-aminopropyltrimethoxysilane,2- (3,4-Epoxy cyclohexyl)Examples thereof include ethyltrimethoxysilane, and one or more organic alkoxysilanes are used in combination.
[0017]
The organic alkoxysilane here is particularly preferably methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, or phenyltriethoxysilane. The partial condensate produced by hydrolysis of the organoalkoxysilane is formed by adding water to the organoalkoxysilane in the composition, and is better than that obtained by hydrolyzing it separately. This hydrolysis condensate acts as a binder as a vehicle.
[0018]
In the composition of the organoalkoxysilane, the blending is 0.7 to 41.7% by weight in terms of hydrolysis and partial condensate, preferably 4.6 to 18.4% by weight and less than 0.7% by weight. The coating film obtained in the above has poor adhesion, physical properties such as satisfactory hardness cannot be obtained, and if it exceeds 41.7% by weight, the coating film is liable to crack and peel off, and the storage stability of the composition is poor. It is better to avoid it.
[0019]
Colloidal zirconia having a pH of 2 to 10 in which water or / and an organic solvent is used as a dispersion medium is superior in heat resistance and adhesion compared to colloidal silica, in particular, thermal shock characteristics specific to zirconia, improved hardness of the coating, and excellent adhesion properties. Is a core raw material of the product of the present invention. The size of the colloidal zirconia particles is 5 to 100 nm, preferably 5 to 80 nm. The amount of colloidal zirconia is 0.27 to 18.6% by weight, preferably 1.4 to 5. 6% by weight. When the blending amount of the colloidal zirconia is less than 0.27% by weight in terms of solid content, the adhesive strength and hardness may be reduced, and the coating film may be cracked. A phenomenon may occur in which the transparency characteristics are deteriorated.
[0020]
Colloidal alumina having a pH of 2 to 10 containing water or / and an organic solvent as a dispersion medium is added to give the excellent hardness and wear resistance characteristics of alumina, and the viscosity of the coating composition due to the viscosity change characteristics of colloidal alumina. It is also used for the purpose of improving and stabilizing paint by positive charge distribution on the surface. The average particle size of the alumina is preferably 5 to 100 nm, and the blending amount is 0.02 to 3.8% by weight, preferably 0.2 to 0.8% by weight in terms of solid content. When the blending amount of the colloidal alumina is less than 0.02% by weight in terms of solid content, the properties of hardness and wear resistance are deteriorated, and when it exceeds 3.8% by weight, the viscosity is rapidly increased and the coating is agglomerated. Is done.
[0021]
The colloidal inorganic pigment using water or / and an organic solvent as a dispersion medium is composed of one or more compounds such as oxides, nitrides, sulfides and cadmium oxides having a pH of 2 to 10, and TiO as a single oxide.₂(Titanium oxide, pyrite, rutile), ZnO (zinc oxide, zincation), CoO (cobalt oxide), Cr₂ O ₃(Chromium oxide), Fe₃ O ₄(Ferrite), Fe₂ O ₃, FeO (ferrous oxide, ferric oxide), transition metal single oxides such as CuO (copper oxide), (Cu · Cr) oxide, (Ti · Co) oxide, (T · Ni) oxidation , (Al · Co) oxide, (Co · P) oxide, (Cr · Al) oxide, (Cr · Sn) oxide, (Fe · Zr) oxide, (Fe · Zn) oxide, (Fe · Cr · Zn) oxide, (Fe · Co · Cr) oxide, (Co · Cr · Al) oxide, (Ti · Fe · Zn) oxide, (Cr · Cu · Mn) oxide, 2-4 types of complex oxides such as (Ti · Ni · Co) oxide, (Fe · Cr · Al · Zn) oxide, (Ti · Ni · Co · Al) oxide, and Ti as the nitride Single nitride such as nitride, Zr nitride, (Ti · Al) nitride, 2-3 types of composite nitride such as (Ti · Al · C) nitride, sulfide (Cd · Zn) sulfide and cadmium are (S · Se) cadmium and are classified by pigment number. Black 26, Black 11, White 108, Red 101, Orange 20, Yellow 184 , Yellow 35, green 26, cobalt blue 28, violet 16 and the like. Colloidal inorganic pigments are manufactured using ultra-differential pulverizers with water or organic solvents as the medium, and ultrafine particle pulverization and manufacturing. In addition, sol-gel and pyrosol methods are also used. In order to stabilize the colloid, colloidal inorganic pigments are completed by adjusting the pH, adjusting the solid content, and modifying the organic surface. The particle size of the colloidal inorganic pigment using water or / and an organic solvent as a dispersion medium is 5 to 300 nm on average, and desirably 5 to 100 nm.
[0022]
The colloidal inorganic pigment used to show the colored transparency of the product of the present invention is 0.02 to 27.9% by weight, preferably 3.8 to 15% by weight, in terms of non-volatile content. When the blending amount of the colloidal inorganic pigment is less than 0.02% by weight in terms of solid content, there is no coloring effect, UV blocking effect, and electromagnetic wave absorption effect. , Paint agglomeration occurs.
[0023]
The water in the composition includes 0.6 to 45.4% by weight, more preferably 5.3 to 21% by weight, including water used for colloidal zirconia, colloidal alumina, and colloidal inorganic pigment using water as a dispersion medium. %. Water used as a dispersion medium for the colloidal zirconia, colloidal alumina, and colloidal inorganic pigment undergoes a hydrolysis reaction with an organic alkoxysilane together with an acid catalyst. When the amount of water is less than 0.6% by weight, hydrolysis reaction hardly occurs, and when it exceeds 45.4% by weight, the gloss and film-forming properties are deteriorated, and the coating film due to delayed evaporation of water. Pinholes are generated and chemical resistance is reduced. The water used may be purified water, tap water or the like other than distilled water close to pure if it has a purity that does not adversely affect the coating film.
[0024]
The aliphatic alcohols are added to suppress the condensation of the organic alkoxysilane when the organic alkoxysilane is dissolved to stabilize the composition and excess water present in the system is distilled off azeotropically. In addition, when the coating film is cured, it provides leveling properties of the coating film, ability to adjust by the ambient humidity, and the like. Examples of the alcohol include methanol, ethanol, propanol, isopropanol, n-butanol, and isobutanol, and one or more of these are used. The alcohol used in the present invention includes 15.9 to 95.4% by weight including the alcohol contained in the organoalkoxysilane, colloidal zirconia, colloidal alumina, and colloidal inorganic pigment, and more desirably 34.8 to 76. It is in the range of 5% by weight. When the amount of the aliphatic alcohol is less than 15.9% by weight, it is difficult to produce a reaction at the time of production or a rapid reaction occurs. If it is reduced and exceeds 95.4% by weight, the viscosity and hiding power will be reduced, the reaction will not easily occur, it will not be recognized as a coating film due to its very low non-volatile content, and the latent heat of vaporization of the solvent during coating and coating setting As a result, moisture is absorbed and the transparency of the coating film decreases.
[0025]
The inorganic acid and / or organic acid is used as a hydrolysis catalyst when the organic alkoxysilane is hydrolyzed, and is added in an amount of 0.01 to 3% by weight. As the acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, benzoic acid, p-toluenesulfonic acid, citric acid and the like are used. The inorganic acid and organic acid used for the hydrolysis of the present composition are used alone or in combination of two or more to adjust the pH to 2-7. When the acid concentration is high, the reaction rate rapidly increases, and there are problems such as a severe exothermic reaction and easy gelation. On the other hand, when the temperature is too low, the reaction does not easily occur, and at low temperatures, gelation easily occurs without heat of reaction.
[0026]
The present invention will be described in detail with reference to examples.
(Example 1)
[Test material / surface pretreatment]
Materials used in the present invention include metals such as titanium steel, stainless steel, aluminum and aluminum alloys, ceramics such as glass and tiles, plastics such as polycarbonate, acrylic and PET, and paper.
[0027]
Further, the pretreatment of the material can be classified into a physical method, a chemical method, a primer method and the like. Physical methods include sand blasting, short blasting, dry ice blasting, hairline, and vibration. Chemical methods include aluminum vapor deposition, anodized film, electrolytic coloring, and alkaline degreasing for final cleaning in all tests. The primer treatment is used when adhesion to an inorganic paint such as plastic is impossible, and silk screen printing for the purpose of thermal equipment, various decorations and signs is used as an undercoat.
[0028]
Table 1 shows the pretreatment method and classification according to material, and the kind of material and the pretreatment method of the present invention are not limited in the material and pretreatment methods a1 to j3 used in the present invention.
[Coating composition / manufacturing]
Specific blending examples relating to the coating composition of the present invention are shown in the coating compositions A to R in Tables 2 to 4. A general method for producing / synthesizing the coating composition of the present invention is as follows.
[Mixed liquid A production]
Colloidal zirconia or / and colloidal alumina or / and colloidal inorganic pigment containing organic alkoxysilane and alcohol as a dispersion medium are mixed, placed in a container of about 0.5 liter, and stirred at a speed of about 500 to 800 rpm for 5 ±. The mixture A is produced by maintaining at 3 ° C., or suppressing / maintaining the reaction from the mixture.
[Mixed liquid B production]
On the other hand, colloidal zirconia or / and colloidal alumina or / and colloidal inorganic pigment and water which is the dispersion medium of water in another 1.5 liter reaction vessel are added, and the reaction catalyst is stirred while stirring at a speed of about 500 to 800 rpm. Acid (inorganic acid and / or organic acid) is added to pH = 2-7, and the temperature of the stirring liquid is maintained at 10 ± 5 ° C. to prevent aggregation of colloidal particles due to exothermic reaction of the liquid mixture. B is manufactured.
[Mixed liquid A + B production]
The produced mixed solution B is stirred at a speed of about 500 to 800 rpm, the temperature of the stirred solution is maintained at 25 ± 5 ° C., and the previously produced mixed solution A is about 5 to 20 cc per minute and the exothermic reaction temperature is 25. Add dropwise while adjusting to ± 5 ° C. After the dropping of the liquid mixture A is completed, stirring is maintained for about 30 to 90 minutes. In order to adjust the non-volatile content according to the coating method, alcohol is added and then sealed and aged at room temperature (25 ° C.) for 1 to 4 hours for coloring. A transparent inorganic coating composition is produced. In the case of the coating composition (P and Q) applied to plastic among the coating compositions, lithium acetate and formic acid were mixed and dissolved at a ratio (weight ratio) of 2: 3 in order to promote low temperature curing. The solution is added in an amount of 3 to 5% by weight based on the nonvolatile content of P and Q.
[0029]
Composition examples A to R used in the present invention do not limit the colored transparent inorganic coating composition of the present invention, and the methods for producing the A and B liquids are not limited by the examples. That is, a colloidal inorganic pigment using organic alkoxysilane and alcohol as a dispersion medium is stirred and mixed to produce a mixed solution A, and water and a reaction catalyst are mixed with acid (inorganic acid or colloidal zirconia and colloidal alumina using water as a dispersion medium. / And organic acid) may be added and stirred and mixed to produce liquid mixture B. Finally, the hydrolyzate and condensation of organic alkoxysilane whose coating composition is 0.7 to 41.7% by weight The average size of the particles using water or alcohol as a dispersion medium is 5 to 100 nm, 0.27 to 18.6% by weight of colloidal zirconia in terms of solid content, and water or alcohol as a dispersion medium. The average particle size is 5 to 100 nm, and the average particle size is 5 to 3 in terms of solid content, using 0.02 to 3.8% by weight of colloidal alumina and water or alcohol as a dispersion medium. The colloidal inorganic pigment is 0.02 to 27.9% by weight in terms of solid content and is contained in colloidal zirconia, colloidal alumina, and colloidal inorganic pigment using water as a dispersion medium. 45.9% by weight of water, 15.9 to 95.4% by weight of lower aliphatic contained in colloidal zirconia, colloidal alumina, and colloidal inorganic pigment containing the alcohol contained in the organoalkoxysilane and the alcohol as a dispersion medium A production method comprising an alcohol and an acid used for a hydrolysis catalyst of 0.01 to 3% by weight is included.
[Coating method and curing method]
The general spray coating, electrostatic coating, dip coating, roll coating (including bar coating), flow coating, brush coating, etc. are all possible for the coating method used in the present invention. The curing method used in the present invention can be raised to a maximum of 180 ° C, such as conveyor type or belt type LPG, petroleum, electric heating type continuous oven, arrangement type box oven, mechanical convection oven, constant temperature and humidity chamber. Any heating method is possible. Specific examples of the coating method and the curing method are shown in Table 5. The coating method and the curing method Z-1 to Z-10 used in this example do not limit the coating method and the curing method.
[Appearance and physical property test results of coating film]
Preparation of materials by test materials and surface pretreatment of Table 1 and preparation of coating materials by coating compositions of Tables 2 to 4, and coating films by coating methods and curing methods of Table 5 were formed. The appearance evaluation of the coating film accompanying with is shown.
[0030]
Tables 8 and 9 show test methods for the products of the present invention. Tables 10 to 17 show the overall physical properties of the coating films of the present products according to the test methods. The symbol “0” is “no abnormality” in the results of the comprehensive physical properties of the paint film.
Or “no contamination”.
[0031]
[Table 1]

* (1) Japan, Nippon Steel Corporation products, titanium steel plate
* (2) Japan, Nippon Steel Co., Ltd. product, stainless steel plate, SUS-304
* (3) 3 mm: Korea, Korea Aluminum Co., Ltd. product, aluminum alloy steel plate, A3003
15 μm: Korea Sanya Aluminum Co., Ltd. product, cooking foil
* (4) Korea, Doosan Packaging Co., Ltd. product, fruit juice container, transparent (uncolored glass)
* (5) Korea, Korea Glass Co., Ltd., commercially available flat glass
* (6) Korea, Taiho Ceramics Co., Ltd. products, commercially available white tiles
* (7) US, General Electric Co., Ltd. product, Lexan
* (8) Korea, LG Chemical Co., Ltd. products
* (9) Products from Korea, Sanyosha Co., Ltd.
* (10) Paper fans / cups: Korean Keiichi Packaging Co., Ltd. products, pound cups, baking fans
Pulp mold: Korean Resite Co., Ltd.
* (11) Sand blasting machine is used, sanding sand: 100 mesh, sanding roughness: 2-3 μm
* (12) Using a short blasting device, short ball: 0.5 mm stainless steel ball, short roughness: 1-2 μm
* (13) Use dry ice blast (Japan, Nippon Oxygen Co., Ltd., Magic Blast), short agent: dry ice pellets
* (14) Hairline processing by continuous polishing method of abrasive on the surface of stainless steel plate
* (15) Surface processing by vibration polishing of metal steel plate surface
* (16) Korea, Imex Co., Ltd. product, aluminum vacuum-deposited glass cup (pattern deposition), glass cross-section deposition
* (17) Aluminum alloy, A3003, anodized, alumite film thickness: 12 μm, unsealed
* (18) Electrolytic coloring (5 colors including black, bronze, blue, gold, red, green) by chemical treatment of stainless steel and titanium steel, and buoyancy treatment coating with chemical solution. 0.25 μm
* (19) Korea, Nankoku Kako Co., Ltd., Nabachem NB-1 deposited or rubbed and washed, then removed with 5 ° C distilled water and dried.
* (20) Spraying / dipping application to Japan, Toshiba Silicon Corporation products, primer PH-91 (acrylic, for PET), PH-93 (for polycarbonate), drying at 30-40 ° C for 10 minutes
* (21) Korea, Korea Fine Ceramics Co., Ltd., silk screen (# 250) printing with Ceraink CI-300, dried at room temperature and / or 30-40 ° C for 20 minutes or more
[0032]
[Table 2]

** (1) Japan, Toshiba Silicon Corporation, Japan, Shin-Etsu Corporation products
** (2) Japan, Nissan Chemical Co., Ltd., USA, Nyakor Co., Ltd., USA, Nanoface Co., Ltd., Japan, Fuji Pigment Co., Ltd.
** (3) Japan, Nissan Chemical Co., Ltd., USA, Nyacor Corporation, USA, Nanoface Corporation, Germany, Tegusa Corporation
** (4) Japan, Nissan Chemical Co., Ltd., USA, Nyacoal Corporation, USA, Nanoface Corporation, Japan, Fuji Pigment Corporation products
[0033]
[Table 3]

[0034]
[Table 4]

[0035]
[Table 5]

*** (1) Use of general air spray (W-61, Japan, Iwata Co., Ltd. product)
*** (2) A high voltage electrostatic spray device using Japan, Lanceberg Industry Co., Ltd., Inverter Reciprocator and Microbell 96 is used under the following setting conditions.
-Discharge rate: 80 to 115 cc / min
-Conveyor speed: 1.5 to 1.6 m / min
-Applied voltage: 60 kV
-Number of revolutions: 17,000-20,000 rpm
-Stroke: 600mm
-Stroke speed: 30-40 m / min
***(3) A method in which a test specimen immersed in a coating agent is pulled up at a constant speed and coated using a pulling machine.
***(4) In the roll coating, a bar coater (Bar Coater) was used experimentally, and the calculation was performed by “bar coater number × 3/2 = wet coating thickness”.
[0036]
[Table 6]

*** (1) UV-VIS spectrometer, spectral transmittance in the visible light region
[0037]
[Table 7]

[0038]
[Table 8]

*** (1) KS, JIS, and ASTM are industrial standards of Korea, Japan, and the United States, respectively.
*** (2) American Architectural Manufacturer Association Coating Film Testing Method
[0039]
[Table 9]

[0040]
[Table 10]

[0041]
[Table 11]

[0042]
[Table 12]

[0043]
[Table 13]

[0044]
[Table 14]

[0045]
[Table 15]

[0046]
[Table 16]

[0047]
[Table 17]

[0048]
[Table 18]

＊＊＊＊＊＊ (1) Ultraviolet resistance: UV lamp (Japan, Toshiba Corporation product, black light 4WFL4BL-B) put a glass cup at a distance of 5cm vertically and investigated for 128 hours)
[0049]
[Table 19]

＊＊＊＊＊＊＊ (1) Discoloration promotion test: Confirmation of discoloration by deposition in nitric acid solution at 60 ℃ for 10 days
[0050]
[Table 20]

＊＊＊＊＊＊＊＊ (1) Deposition of the pound cup in the water / 1 hour later
＊＊＊＊＊＊＊＊ (2) Arsenic (within limits), heavy metal (within 10 ppm), formaldehyde (within limits), optical brightener (not detected), tar dye (not detected), residual evaporation (30 mg) / L or less)
＊＊＊＊＊＊＊＊ (3) Whether or not the paper pound cup can be discolored and whether or not the oven can be used when baking a cake in a bakery oven (200-300 ° C)
[Example 2]
After forming an aluminum vapor deposition pattern on a colorless transparent glass cup, alkali degreasing was performed, and pre-treatment of the decorative glass cup (Korean Imex Co., Ltd. product) was completed. Pre-processing similar to that for the piece number d3). The colored transparent inorganic coating composition is made into the G composition shown in Table 3, and is a colored transparent coating made by adding a Japon dye (product of Pasf, Germany, Japon Orange 244) to a commercially available acrylic baking resin. The coating and curing methods of the composition and the comparative example are performed in the process of Z-3 in Table 5, and FIG. 2 shows photographs before and after the treatment of the colored transparent inorganic coating composition. Table 18 shows the test results of the appearance and physical properties of the coating film. In the physical property results of the coating film, the symbol “0” indicates “no abnormality” or “no discoloration”, and “x” indicates “bad” or “decoloration”.
[Example 3]
Kitchen container made of stainless steel plate (Korean, ARTDEMAJON Co., Ltd. product, size: 30cm diameter x 20cm depth) The surface was polished and then degreased with alkali to complete pretreatment of stainless steel kitchen container (test of Table 1) The same pretreatment as that for the specimen number b1 is performed during the preparation of the material and the surface pretreatment. The colored transparent inorganic coating composition has the G composition shown in Table 3, and the coating and curing method is performed in the process of Z-3 in Table 5. In comparison, a commercially available product whose surface is polished with stainless steel is used. FIG. 5 shows photographs of the colored transparent inorganic coating composition before and after treatment, the appearance of the coating film and the physical property test results of the coating film are shown in Table 19, and FIG. 6 shows the result of the discoloration acceleration test. In the physical property results of the coating film, the symbol “0” indicates “no abnormality” or “no discoloration”, and “x” indicates “discoloration”.
[Example 4]
Prepare a paper pound cup (Keioichi Co., Ltd. product, pound cup) and make it the 0 composition in Table 3 of the colored transparent inorganic paint composition. The coating and curing method is the colored transparent inorganic paint in the process of Z-2 in Table 5 2 types of paper-pound cups coated with (a double-sided treatment that coats the inside and outside of the cup and an internal surface treatment that coats only the inside of the cup), and prepares a commercially available untreated paper pound cup for the comparative example To do. The dough of the cake is put into a pound cup treated with the product of the present invention and an untreated pound cup and baked in an oven at 200 to 250 ° C. for about 20 minutes, and then compared with other physical property evaluations (see FIG. 7). The test results of the appearance of the coating film and the physical properties of the coating film are shown in Table 20, and the far infrared radiation comparison graph is shown in FIG. In the physical property results of the coating film, the symbol “0” indicates “no abnormality” or “good”, and “x” indicates “dipping” or “bad”.
[0051]
The present invention is not limited to the specific preferred embodiments described above, and does not fall out of the gist of the present invention claimed in the scope of claims. Anyone who has ordinary knowledge in the technical field to which the present invention belongs can implement various modifications. Of course, variations thereof are within the scope of the claims.
[0052]
【The invention's effect】
The present invention uses a colloidal inorganic pigment and, together with the coloring transparency effect of the coating film, is stable without any discoloration or discoloration even when exposed to high heat and ultraviolet rays for a long time, and maintains the texture of the metal surface as it is. By providing the protection of the metal surface at the same time, there are no problems arising from methods such as plating, electrolytic coloring, and sputtering, that is, there is no size limitation, drainage contamination, color unevenness, etc. Work can be saved.
[0053]
That is, the coating film formed by coating the surface of a base material such as metal, plastic, glass, paper, etc. according to the present invention, the colored transparent inorganic coating composition, has a partial wavelength of visible light and ultraviolet light. Excluded, most of them are transparent, and various colored transparency effects are obtained from black, white, red, yellow, green, blue and purple.
[0054]
In addition, when the present invention is coated and cured on the surface of metal substrates, glasses, paper, etc., it has a beautiful appearance, weather resistance, and stain resistance as compared with colored paints and dyeing types to which organic coloring pigments are added. High hardness, water resistance, adhesion, corrosion resistance, durability, etc. are excellent.
[0055]
With such functional characteristics, it can be expected that a coating film for a wide range of applications will be formed throughout the industry such as architectural interior / exterior agents and thermal equipment, and that it will be replaced with a new material that is wide and functional with limited materials.
[0056]
In addition, the characteristics of the colloidal inorganic pigment and oxide used in the present invention, that is, the characteristics of absorption of ultraviolet rays other than visible light, emission of far infrared rays, and absorption of electromagnetic waves can be applied to various substrates.
[0057]
When the present invention is applied to the surface of a plastic substrate, it completely blocks ultraviolet rays from reaching the substrate surface, and the surface hardness is improved to protect the article on the substrate and the back surface of the substrate from the ultraviolet rays and the external environment.
[0058]
When the present invention is applied to aluminum cooking foils and papers, a high far-infrared radiation effect and non-adhesive properties can be obtained, and it can be used in a heating container that can be used in a microwave oven.
[0059]
By enabling full-scale realization of the transparent color, that is, the third color, in the fields of architectural interior and exterior materials and industrial applications that depended on the existing solid color and metallic color, that is, solid color And metallic color combined with the colored transparent color of the colored transparent composition of the present invention makes it possible to realize a hue that is unimaginable, which has a great impact on the technical capabilities of national flag architecture and industrial design and national flag colors. Expected to affect.
[0060]
In addition to the physical properties of the inorganic paint of the composition of the present invention, optical properties, that is, UV blocking, far-infrared emission or heat ray reflection utilizing the absorption and emission characteristics of the intrinsic wavelength of the colored transparent inorganic pigment. By providing the electromagnetic wave absorbing function, there are many effects such as transparent and harmful ultraviolet ray blocking, heat ray reflection / emission, electromagnetic wave blocking / absorption, transparent material / functional material can be easily adopted only by surface coating treatment.
[Brief description of the drawings]
FIG. 1 is a photograph of a titanium steel plate (surface vibration pretreatment) of the present invention before and after a colored transparent composition coating treatment (left is before treatment, and right is after treatment).
FIG. 2 is a photograph of the stainless steel plate of the present invention (surface hairline pretreatment) before and after the colored transparent composition coating treatment (left side before treatment, right side after treatment).
FIGS. 3A and 3B are photographs before and after a colored transparent composition coating treatment on the colorless and transparent glass bottle (degreasing pretreatment) of the present invention (the upper row is before treatment and the lower row is after treatment).
FIGS. 4A and 4B are photographs before and after the colored transparent composition coating treatment on the decorative cup (surface aluminum pattern pre-deposition treatment) of the present invention (the left side is before treatment and the right side is after treatment).
FIG. 5 is a photograph of the stainless steel pan (surface gloss polishing, pre-degreasing pretreatment) of the present invention before and after the colored transparent composition coating treatment (left side before treatment, right side after treatment).
FIG. 6 is a result of a discoloration acceleration test result before and after the colored transparent composition coating treatment of the stainless steel pan of the present invention.
FIG. 7 is a baking photograph of a paper baking cup according to the present invention before and after coating with a colored transparent composition (double-side treatment on the left side, inner surface treatment on the center, and untreated on the right side).
[Fig. 8] Far-infrared radiation (W / cm) according to temperature of paper baking cup²) Measurement comparison result diagram.

Claims

0.7 to 41.7% by weight of an organoalkoxysilane hydrolyzate and condensate;
The average particle size of water and / or alcohol as a dispersion medium is 5 to 100 nm, the pH is 2 to 10, and the colloidal zirconia is 0.27 to 18.6% by weight in terms of solid content,
The average particle size of water and / or alcohol as a dispersion medium is 5 to 100 nm, the pH is 2 to 10, and 0.02 to 3.8% by weight of colloidal alumina in terms of solid content,
Colloidal inorganic pigment having an average particle size of 5 to 300 nm in water and / or alcohol as a dispersion medium, and 0.02 to 27.9% by weight in terms of solid content,
A colored transparent inorganic coating composition comprising 0.01 to 3% by weight of an acid used for a hydrolysis catalyst,
At least one of the colloidal zirconia, the colloidal alumina, and the colloidal inorganic pigment contains water,
The weight percentage of water contained in the colored transparent inorganic coating composition is 0.6 to 45.4% by weight,
The colored transparent inorganic coating composition, wherein the weight percentage of alcohol contained in the colored transparent inorganic coating composition is 15.9 to 95.4% by weight.

The organic alkoxysilane is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, n-propyltriethoxysilane, γ-chloro. Propyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxy Of propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, phenyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane One or colored transparent inorganic coating composition according to claim 1, characterized in that the combination and use of two or more selected from.

2. The colored transparent inorganic paint according to claim 1, wherein the inorganic pigment is composed of one or more compounds selected from oxides, nitrides, sulfides, and cadmium compounds having a pH of 2 to 10. 3. Composition.

The oxides are TiO ₂ (titanium oxide, pyrite, rutile), ZnO (zinc oxide), CoO (cobalt oxide), Cr ₂ O ₃ (chromium oxide), Fe ₃ O ₄ (ferrite), Fe ₂ O. ₃ , FeO (ferrous oxide, ferric oxide), CuO (copper oxide), (Cu · Cr) oxide, (Ti · Co) oxide, (Al · Co) oxide, (Co · P) Oxide, (Cr · Al) oxide, (Cr · Sn) oxide, (Fe · Zr) oxide, (Fe · Zn) oxide, (Fe · Cr · Zn) oxide, (Fe · Co · Cr) oxide, (Co · Cr · Al) oxide, (Ti · Fe · Zn) oxide, (Cr · Cu · Mn) oxide, (Ti · Ni · Co) oxide, (Fe · Cr · It is selected from the group consisting of (Al · Zn) oxide and (Ti · Ni · Co · Al) oxide. Colored transparent inorganic coating composition according to claim 3.

4. The colored transparent according to claim 3 , wherein the nitride is selected from the group consisting of Ti nitride, Zr nitride, (Ti · Al) nitride, and (Ti · Al · C) nitride. Inorganic coating composition.

The colored transparent inorganic coating composition according to claim 3 , wherein the sulfide is (Cd · Zn) sulfide.

The colored transparent inorganic coating composition according to claim 3 , wherein the cadmium compound is (S · Se) cadmium compound.

The colored transparent inorganic coating composition according to claim 1, wherein the acid is used in combination of one or more inorganic acids or organic acids.

The acids are hydrochloric, sulfuric, nitric, phosphoric, formic, acetic, benzoic acid, p-toluenesulfonic acid, according to claim 1 or claim 8, characterized in that selected for use from among citric acid Colored transparent inorganic coating composition.

A step of stirring and mixing an organic alkoxysilane and a colloidal inorganic pigment having an average particle size of 5 to 300 nm using alcohol as a dispersion medium;
A colloidal zirconia having an average particle diameter of 5 to 100 nm using water as a dispersion medium, colloidal alumina having an average particle diameter of 5 to 100 nm using water as a dispersion medium, and an acid contained in the colloidal zirconia and the colloidal alumina. B step of adding an acid as a hydrolysis catalyst of the organoalkoxysilane, stirring and mixing;
C step of dripping and reacting with the liquid produced in step a while stirring the liquid produced in step b, and maintaining stirring for about 30 to 90 minutes after completion of the reaction;
The liquid produced in step c is filled with an alcohol containing alcohol generated in the hydrolysis reaction of the organoalkoxysilane in step a and alcohol contained in the colloidal inorganic pigment by a coating method, and then sealed. A method for producing a colored transparent inorganic coating composition comprising d stage aging at room temperature (25 ° C.) for about 1 to 24 hours,
The weight percentage of the hydrolyzate and condensate of the organoalkoxysilane contained in the colored transparent inorganic coating composition is 0.7 to 41.7% by weight,
The percentage by weight of the solid content of the colloidal zirconia contained in the colored transparent inorganic coating composition is 0.27 to 18.6% by weight,
The weight percentage of the solid content of the colloidal alumina contained in the colored transparent inorganic coating composition is 0.02 to 3.8% by weight,
The weight percentage of the solid content of the colloidal inorganic pigment contained in the colored transparent inorganic coating composition is 0.02 to 27.9 wt%,
The weight percentage of water contained in the colored transparent inorganic coating composition is 0.6 to 45.4% by weight,
The weight percentage of alcohol contained in the colored transparent inorganic coating composition is 15.9 to 95.4% by weight,
Weight percentage of acid contained in the colored transparent inorganic coating composition, Ri 0.01-3 wt% der,
Wherein the colloidal zirconia, and the colloidal alumina contained in the colored transparent inorganic coating composition, method for producing a colored transparent inorganic coating composition is PH2～10.

The mixture b step method for producing a colored transparent inorganic coating composition according to claim 10, characterized in that the pH 2-7.

0.7 to 41.7% by weight of an organoalkoxysilane hydrolyzate and condensate;
Colloidal zirconia having an average particle size of 5 to 100 nm in water and / or alcohol as a dispersion medium and a pH of 2 to 10 and 0.27 to 18.6% by weight in terms of solid content,
The average particle size of water and / or alcohol as a dispersion medium is 5 to 100 nm, the pH is 2 to 10, and 0.02 to 3.8% by weight of colloidal alumina in terms of solid content,
A colloidal inorganic pigment having an average particle size of 5 to 300 nm in water and / or alcohol as a dispersion medium, and 0.02 to 27.9 wt% in terms of solid content;
A coating method using a colored transparent inorganic coating composition, which comprises applying a colored transparent inorganic coating composition containing 0.01 to 3% by weight of an acid used for a hydrolysis catalyst,
At least one of the colloidal zirconia, the colloidal alumina, and the colloidal inorganic pigment contains water,
The weight percentage of water contained in the colored transparent inorganic coating composition is 0.6 to 45.4% by weight,
The coating method using the colored transparent inorganic coating composition, wherein the weight percentage of alcohol contained in the colored transparent inorganic coating composition is 15.9 to 95.4% by weight.