JP4578783B2 - Solvent-free surface treatment agent for inorganic substrate, and method for surface treatment of inorganic substrate using the treatment agent - Google Patents
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Description
【０００１】
【発明の技術分野】
本発明は、無溶剤型の無機質基材用下地処理剤および該処理剤を用いた無機質基材の下地処理方法に関する。
【０００２】
【発明の技術的背景】
従来から、無機質基材は、不燃建材板として内外装、屋根等に広く使用されている。しかしながら、無機質基材は、その材質がアルカリ性であるため、基材表面にアルカリ分の染み出し〔白華（エフロレッセンス）〕を発生する恐れがあり、これを防止する必要がある。さらに、該基材表面の粉化を防止し、脆部を固化・強化等する必要もある。したがって、無機質基材表面を塗装する場合、一般的に、まず表面にシーラー塗装を施し、さらに美観等を目的として上塗り塗装を施すことにより塗装作業を行う。
【０００３】
上記無機質基材のシーラー塗装は、従来から、基材表面に含浸シーラー塗装（下地処理）を行った後に、下塗り塗装を行うことにより行われている。そのような無機質基材のシーラー塗装は、具体的には、まず、シーラー塗膜と無機質基材とを強固に付着させるために、無機質基材表面に多量の溶剤で希釈されたイソシアネート溶液やエポキシ樹脂溶液を含浸シーラー（下地処理剤）として塗布し、その後基材を隠ぺいする下塗り塗料を塗布することにより行われている。
【０００４】
また、その他の無機質基材のシーラー塗装としては、溶剤系常温硬化（反応）型樹脂塗料、例えば２液型アクリルウレタン樹脂塗料を無機質基材に塗布し、含浸シーラー塗装と下塗り塗装とを１工程で行う無機質基材のシーラー塗装方法が提案されている（例えば、特許文献１参照。）。
【０００５】
しかしながら、近年、有機溶剤による大気汚染、水質汚染、土壌汚染などの環境汚染や、人体への影響が懸念されるにつれ、無機質基材の含浸シーラー塗装（下地処理）においても有機溶剤を使用しない塗料組成物が求められてきている。
【０００６】
そのような問題を解決するものとして、乳化性親水基含有イソシアネートプレポリマーを多量の水に希釈した水系の下地処理剤を用いた無機質基材の下地処理方法が提案されている（例えば、特許文献２参照。）。
【０００７】
しかしながら、このような乳化性親水基含有イソシアネートプレポリマーから形成される下地処理膜は、水との親和性が高いため、このプレポリマーで下地処理された無機質基材は、耐水性、耐温水性等に改良の余地があった。
【０００８】
また、無機質基材は、その種類によって密度が異なるため、下地処理剤を所望の深さまで浸透させることができない場合がある。そのような場合、下地処理された無機質基材の密度に応じて、耐水性、耐温水性等が不十分となることがあった。
【０００９】
【特許文献１】
特許第２８０８３９９号公報
【特許文献２】
特開平６−９２７５６号公報
【００１０】
【発明の目的】
本発明は、上記のような従来技術に伴う問題点を解決しようとするものであって、塗装作業における作業性および安全性が高く、各種の無機質基材への浸透性や付着性に優れ、さらに耐水性、耐温水性等に優れた下地処理膜を形成することができる無溶剤型の無機質基材用下地処理剤、および該処理剤を用いた無機質基材の下地処理方法を提供することを目的としている。
【００１１】
【発明の概要】
（１）粘度が１５０ｍＰａ・ｓ（２５℃）以下であるイソシアネート化合物からなること特徴とする無溶剤型の無機質基材用下地処理剤。
（２）前記イソシアネート化合物が、リジンジイソシアネート、またはリジントリイソシアネートであること特徴とする（１）に記載の下地処理剤。
（３）前記イソシアネート化合物が、ヘキサメチレンジイソシアネートまたはジフェニルメタンジイソシアネートから得られるポリイソシアネートまたはそのプレポリマーであること特徴とする（１）に記載の下地処理剤。
（４）前記（１）〜（３）のいずれかに記載の無機質基材用下地処理剤から形成されたこと特徴とする下地処理膜。
（５）無機質基材の表面を、前記（１）〜（３）のいずれかに記載の無機質基材用下地処理剤で下地処理すること特徴とする無機質基材の下地処理方法。
（６）無機質基材の表面を、前記（１）〜（３）のいずれかに記載の無機質基材用下地処理剤で下地処理し、該処理で形成された下地処理膜の表面に下塗り塗装を施すこと特徴とする無機質基材の塗装方法。
（７）前記下塗り塗装で形成された下塗り層の表面に、柄付けを施すこと特徴とする（６）に記載の無機質基材の塗装方法。
（８）前記下塗り塗装で形成された下塗り層の表面に、上塗り塗装を施すこと特徴とする（６）に記載の無機質基材の塗装方法。
（９）前記柄付けを施すことにより得られた柄付け済み下塗り層の表面に、上塗り塗装を施すこと特徴とする（７）に記載の無機質基材の塗装方法。
（１０）前記上塗り塗装に用いられる塗料組成物が、アクリル系塗料組成物、エポキシ系塗料組成物、またはウレタン系塗料組成物であること特徴とする（８）または（９）に記載の無機質基材の塗装方法。
（１１）前記上塗り塗装に用いられる塗料組成物が、紫外線硬化性の塗料組成物であること特徴とする（８）または（９）に記載の無機質基材の塗装方法。
（１２）前記（５）に記載の無機質基材の下地処理方法により製造されたこと特徴とする下地処理膜付き無機質基材。
（１３）前記（６）〜（１１）のいずれかに記載の方法により製造されたこと特徴とする塗膜付き無機質基材。
【００１２】
【発明の具体的説明】
以下、本発明について具体的に説明する。
【００１３】
まず、本発明に係る無溶剤型の無機質基材用下地処理剤（以下、単に「無機質基材用下地処理剤」とも言う）について説明する。
【００１４】
無溶剤型の無機質基材用下地処理剤
本発明に係る無溶剤型の無機質基材用下地処理剤は、
粘度が１５０ｍＰａ・ｓ（２５℃）以下であるイソシアネート化合物からなり、実質的に有機溶剤や水を含有しない下地処理剤である。この下地処理剤は、実質的に有機溶剤を含有しないので塗装作業における安全性が高い。
【００１５】
以下、上記成分について説明する。
【００１６】
イソシアネート化合物
本発明に用いられるイソシアネート化合物は、その粘度（２５℃）が、１５０ｍＰａ・ｓ以下、好ましくは５０ｍＰａ・ｓ以下、さらに好ましくは１０〜２５ｍＰａ・ｓであることが望ましい。粘度の測定は、Ｂ型粘度計を用い、液温２５℃により行った。
【００１７】
このような範囲の粘度であることにより、得られる無溶剤型の無機質基材用下地処理剤は、無機質基材の種類に関わらず、無機質基材に所望の深さまで浸透させることができる。すなわち、本発明の無溶剤型の無機質基材用下地処理剤は密度が異なる無機質基材に対しても、充分に浸透することができる。したがって、本発明の前記下地処理剤は、各種の無機質基材に耐水性、耐温水性等を充分に付与することができる。
【００１８】
このイソシアネート化合物１００重量％には、イソシアネート基が、２０〜５０重量％、好ましくは３０〜４０重量％の量で残存していることが望ましい。残存するイソシアネート基が、上記範囲にあると、無溶剤型の無機質基材用下地処理剤からなる塗膜と無機質基材との接着性が優れ、さらに塗膜の耐水性、耐温水性が向上するため好ましい。
【００１９】
このような本発明に用いられるイソシアネート化合物としては、ジイソシアネートやトリイソシアネートなどのイソシアネートモノマー、またはこのイソシアネートモノマーから得られるポリイソシアネートまたはそのプレポリマーなどが挙げられる。
【００２０】
上記ジイソシアネートとしては、具体的には、4,4'-ジフェニルメタンジイソシアネート［ＭＤＩ］、キシリレンジイソシアネート［ＸＤＩ］等の芳香族ジイソシアネート；
メチレンビス（4-シクロヘキシルイソシアネート）［ＨＭＤＩ］、イソホロンジイソシアネート［ＩＰＤＩ］等の脂環式ジイソシアネート；
ヘキサメチレンジイソシアネート［ＨＤＩ］、トリメチルヘキサメチレンジイソシアネート［ＴＭＨＭＤＩ］、リジンジイソシアネート（ＬＤＩ）等の脂肪族ジイソシアネートなどが挙げられる。
【００２１】
上記トリイソシアネートとしては、具体的には、トリフェニルメタントリイソシアネート、リジントリイソシアネート（ＬＴＩ）などが挙げられる。
【００２２】
ジイソシアネートまたはトリイソシアネートとしては、上記粘度範囲であれば特に限定されないが、下記式（Ｉ）に示されるリジンジイソシアネート（ＬＤＩ）、下記式（II）に示されるリジントリイソシアネート（ＬＴＩ）が好ましい。
【００２３】
このようなＬＤＩ、ＬＴＩを用いた無機質基材用下地処理剤は、無機質基材と強固に付着し、さらに耐水性、耐温水性が向上した下地処理膜を形成することができる。
【００２４】
【化１】
上記の式（Ｉ）中、Ｒ1は炭素原子数１〜１２のアルキル基、好ましくは炭素原子数１〜８のアルキル基、さらに好ましくは炭素原子数１〜４のアルキル基が望ましい。
【００２６】
【化２】
上記の式（II）中、Ｒ2は炭素原子数２〜８のアルキレン基、好ましくは炭素原子数２〜４のアルキレン基、さらに好ましくはエチレンであることが望ましい。上記アルキレン基は、ハロゲン原子、炭素原子数１〜４のアルコキシ基、炭素原子数１〜４のアシル基、フェニル基等で置換されていても良い。
【００２８】
また、本発明に用いられるポリイソシアネートまたはそのプレポリマーとしては、上記ジイソシアネートまたはトリイソシアネートから得られる、下記式（III）に示すイソシアヌレート環を有するイソシアヌレート体、ビューレット体、トリメチロールプロパン・アダクト体、アロファネート体などが挙げられる。
【００２９】
【化３】
ポリイソシアネートまたはそのプレポリマーとしては、上記粘度範囲であれば特に限定されない。
【００３１】
このようなポリイソシアネートまたはそのプレポリマーを用いた無機質基材用下地処理剤は、無機質基材と強固に付着し、さらに耐水性、耐温水性が向上した下地処理膜を形成することができる。
【００３２】
本発明に用いられるイソシアネート化合物としては、具体的には、ＬＤＩ〔商品名：協和発酵（株）製、リジンジイソシアネート（上記式（Ｉ）中、Ｒ1がメチル基） 、１１ｍＰａ・ｓ（２５℃）、数平均分子量２１２〕、ＬＴＩ〔商品名：協和発酵（株）製、リジントリイソシアネート（上記式（ＩＩ）中、Ｒ2がエチレン基）、２５ｍＰａ・ｓ（２５℃）、数平均分子量２６７〕、ＳＢＵイソシアネートＪ２４３（商品名：住化バイエルウレタン（株）製、変性ＭＤＩ、２５ｍＰａ・ｓ（２５℃）、数平均分子量３９０）、ＳＢＵイソシアネートＧ４０４Ｒ（商品名：住化バイエルウレタン（株）製、変性ＭＤＩ、５０ｍＰａ・ｓ（２５℃）、数平均分子量４００）、タケネートＤ−１７８Ｎ（三井武田ケミカル（株）製、ＨＤＩアロファネート体、１１０ｍＰａ・ｓ（２５℃） 、数平均分子量４５０）などが挙げられる。
【００３３】
上記のようなイソシアネート化合物は、単独であるいは２種以上組み合わせて用いることができる。
【００３４】
その他の成分
本発明の無溶剤型の無機質基材用下地処理剤は、基本的には、前記粘度範囲にあるイソシアネート化合物からなる。
【００３７】
具体的には、上記イソシアネート化合物を所定の割合で一度あるいは任意の順序で加えて撹拌、混合し均一に溶解・分散等させて無機質基材用下地処理剤を調製することができる。
【００３８】
このような無溶剤型の無機質基材用下地処理剤を用いた、無機質基材の下地処理方法を以下に説明する。
【００３９】
無機質基材の下地処理方法
本発明の無機質基材の下地処理方法は、４０〜６０℃程度になるよう熱風乾燥機等でプレヒートされた無機質基材表面に、上記無溶剤型の無機質基材用下地処理剤を塗布し、下地処理膜を形成することにより行う。
【００４０】
上記無機質基材としては、フレキ板（石綿スレート板）、繊維セメント板、珪酸カルシウム板、石膏ボード、コンクリート板等が挙げられ、表面形状は、平面、凹凸のいずれであってもよい。また、塗装方法としては、スプレー、フローコーター、ロールコーター等の塗装機などにより塗布する方法が挙げられる。
【００４１】
この無溶剤型の無機質基材用下地処理剤の処理量は、基材の密度により異なるが、３０〜６０ｇ／ｍ2、好ましくは、４０〜５０ｇ／ｍ2となる量が望ましい。
３０ｇ／ｍ2未満では下地処理膜と無機質基材との付着が弱く、６０ｇ／ｍ2より多いと、下地処理膜の硬化が遅く作業性に問題がある。
【００４２】
上記のように塗布した後、熱風乾燥機等を用い、熱風６０〜８０℃で１０〜２０分間程度で乾燥し、無機質基材表面に下地処理膜を形成する。
【００４３】
本発明においては、本発明の下地処理剤が無機質基材に所望の深さまで含浸していれば良く、無機質基材表面に形成される乾燥後の下地処理膜の膜厚は、特に限定されないが、通常２０〜５０μｍ（厚）、好ましくは３０〜４０μｍ（厚）であることが望ましい。このような膜厚であることにより、耐水性、耐温水性等に優れた下地処理膜を得ることができる。
【００４４】
この無機質基材用下地処理剤は、上述のイソシアネート化合物を含有している。そのため、イソシアネート化合物のイソシアネート基が、無機質基材表面の水酸基と、さらに無機質基材中の水分とウレタン結合を形成し、この組成物から得られる下地処理膜と無機質基材とが強固に付着すると考えられる。
【００４５】
本発明の無機質基材の下地処理方法は、上記下地処理剤を用いているため、塗装作業における作業性および安全性が高く、各種の無機質基材への浸透性や付着性に優れ、さらに耐水性、耐温水性等に優れた下地処理膜を形成することができる。
【００４６】
本発明においては、このようにして得られた下地処理膜付き無機質基材に、さらに塗装を施す。この無機質基材の塗装方法を以下に説明する。
【００４７】
無機質基材の塗装方法
本発明の無機質基材の塗装方法は、上述のように無機質基材の表面を下地処理した後に、形成された下地処理膜の表面に下塗り塗装を施し、さらに形成された下塗り層の表面に上塗り塗装を施す塗装方法である。
【００４８】
まず以下に、下塗り塗装について説明する。
【００４９】
（下塗り塗装）
下塗り塗装に用いられる下塗り塗料組成物としては、アクリル樹脂塗料組成物、アクリル-ウレタン樹脂塗料組成物、アクリルシリコーン樹脂塗料組成物、酢酸ビニル樹脂塗料組成物、ウレタン樹脂塗料組成物、エポキシ樹脂塗料組成物、アルキッド樹脂塗料組成物など、従来公知の塗料組成物を用いることができる。
これらの下塗り塗料組成物は、溶剤系塗料組成物、水系塗料組成物のいずれであってもよい。
【００５０】
このような下塗り塗料組成物には、これら樹脂と共に、着色顔料、体質顔料、充填剤、防腐剤、防黴剤、耐候安定剤、シリカ等の艶消し材、骨材等が含有されていても良い。上記骨材としては、マイカ、硅砂、ガラスビーズおよびこれらの着色物等が挙げられる。
【００５１】
本発明においては、下塗り塗料組成物は、上記樹脂分と着色顔料等を含有していることが好ましい。
【００５２】
この下塗り塗料組成物の塗装方法としては、スプレー、フローコーター、ロールコーター等の塗装機などにより塗布する方法が挙げられる。上記のように下塗り塗料組成物を塗布した後、従来公知の方法により熱風乾燥、紫外線照射、電子線照射等で乾燥・硬化し、下地処理膜の表面に下塗り層を形成することができる。
【００５３】
このような下塗り層の乾燥膜厚は、特に限定されないが、通常、４０〜７０μｍ厚、好ましくは５０〜６０μｍ厚程度である。
【００５４】
このような下塗り塗料組成物を上記の膜厚となるように塗布することにより、下地処理膜との密着性に優れ、無機質基材表面を隠蔽でき、耐候性に優れ、しかも無機質基材表面への塗料の塗布状況を容易に把握することができる。
【００５５】
また、本発明においては、無溶剤型の無機質基材用下地処理剤からなる被膜表面に、上述のように下塗り塗装を行い、この下塗り層表面にさらに柄付けを行うことが好ましい。
【００５６】
この柄付け方法としては、スクリーン印刷、凸版印刷、フレキソ印刷、平板印刷、グラビア印刷、熱転写等の各種柄付け方法を挙げることができる。これらの柄付けは、従来公知の方法により行われる。
【００５７】
また、本発明においては、下塗り塗料組成物に電子線硬化性の下塗り塗料組成物を用い、下塗り層の硬化と印刷工程とを同時（1工程）に行ってもよい。
【００５８】
このように、上述の無機質基材の下地処理方法によって得られた下地処理膜の表面に、さらに下塗り層（好ましくは、表面が柄付けされた下塗り層）を形成する。本発明の無機質基材の塗装方法においては、この下塗り層表面に、さらに上塗り塗装を施し、上塗り層を形成させる。
【００５９】
以下に、上塗り塗装について説明する。
【００６０】
（上塗り塗装）
この上塗り塗装に用いられる上塗り塗料組成物（たとえばクリアー塗料、カラークリアー塗料）としては、溶剤系塗料組成物、水系塗料組成物のいずれも使用可能であり、下塗り塗料組成物に応じて適宜選択される。
【００６１】
上記溶剤系塗料組成物としては、耐アルカリ性、耐候性などの観点からアクリル樹脂塗料組成物、エポキシ樹脂塗料組成物、ウレタン樹脂塗料組成物、フェノール樹脂塗料組成物、フッ素樹脂塗料組成物、シリコーン樹脂塗料組成物、アクリルシリコーン樹脂塗料組成物等の合成樹脂塗料組成物を用いることができる。
【００６２】
また、上記水系塗料組成物としては、アクリル樹脂塗料組成物、酢酸ビニル塗料組成物、スチレン樹脂塗料組成物、ウレタン樹脂塗料組成物、シリコーン樹脂塗料組成物、アクリルシリコーン樹脂塗料組成物、エポキシ樹脂塗料組成物、フッ素樹脂塗料組成物等の合成樹脂エマルション系塗料組成物を用いることができる。
【００６３】
このような上塗り塗料組成物には、これら樹脂と共に、着色顔料、体質顔料、充填剤、抗菌剤、防腐剤、防黴剤、耐候安定剤、シリカ等の艶消し材、骨材等が含有されていても良い。
本発明に用いられる上塗り塗料組成物としては、アクリル系塗料組成物、エポキシ系塗料組成物またはウレタン系塗料組成物を用いることが好ましい。これらの塗料組成物を用いることにより、耐汚染性、耐薬品性等の良好な表面性能が得られる。
【００６４】
また、本発明に用いられる上塗り塗料組成物としては、光硬化性の塗料組成物であることも好ましい。この光硬化性の塗料組成物としては、ポリエステル（メタ）アクリレート樹脂塗料組成物、エポキシ（メタ）アクリレート樹脂塗料組成物、ポリエーテル（メタ）アクリレート樹脂塗料組成物、ポリウレタン（メタ）アクリレート樹脂塗料組成物等を用いることができる。このような光硬化性の塗料組成物は、硬化速度が速く、作業性に優れるため好ましい。
【００６５】
このような上塗り塗料組成物を用い、下塗り層表面に、ライン塗装、現場施工などにより上塗り塗装を施す。このライン塗装の塗装方法では、通常スプレー、フローコーター、ロールコーター等が使用可能である。現場施工では、前記下塗り塗装板を現場にて施工し、その後、上塗り塗装を施せばよい。
【００６６】
上記のように上塗り塗料組成物を塗布した後、従来公知の方法により熱風乾燥、紫外線照射等で乾燥・硬化し、下塗り層の表面に上塗り層を形成し、本発明の塗膜付き無機質基材を製造することができる。
【００６７】
この上塗り層（硬化膜）の膜厚は、通常４０〜８０μｍ（厚）、好ましくは６０〜７０μｍ（厚）程度であることが望ましい。このように上塗り塗料組成物を上記の膜厚となるように塗布することにより、下塗り層との密着性に優れ、耐候性や耐水性に優れる塗膜付き無機質基材を得ることができる。
【００６８】
また、本発明においては下塗り層表面に上塗り層を形成する態様について説明したが、下塗り層と上塗り層との間に、中塗り塗膜が形成されていてもよい。
【００６９】
このようにして得られる塗膜付き無機質基材は、前記無溶剤型の無機質基材用下地処理剤を用いているため、その表面が非常に平滑となり、いわゆる「仕上がり」の面から優れたものとなる。さらに、本発明の塗膜付き無機質基材は、耐水性、耐温水性に優れ、基材表面への密着性に優れている。したがって、本発明の塗膜付き無機質基材は、内外装、屋根等に用いることができ、特に、浴室、洗面所、キッチンなどの水回りの建築資材に好適に使用される。
【００７０】
【発明の効果】
本発明によれば、塗装作業における作業性および安全性が高く、各種の無機質基材への浸透性や付着性に優れ、さらに耐水性、耐温水性等に優れた下地処理膜を形成することができる無溶剤型の無機質基材用下地処理剤、および該処理剤を用いた無機質基材の下地処理方法を提供することができる。
【００７１】
【実施例】
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００７２】
以下の実施例、比較例で「部」とあるのはすべて重量部を意味する。
【００７３】
なお、実施例および比較例で得られた無溶剤型の無機質基材用下地処理剤、塗膜付き無機質基材は以下の基準に従って評価した。
【００７４】
（１）下地処理剤の粘度
測定条件：Ｂ型粘度計、液温２５℃
（２）下地処理剤の皮膚刺激性
うさぎの皮膚（２５ｍｍ×２５ｍｍ）に、下地処理剤を０．５ｍｌ付着させ、２４時間経過後の皮膚刺激性を、以下の基準に従い目視にて評価した。
【００７５】
３点：刺激性が弱い
２点：刺激性がやや強い
１点：刺激性が強い
（３）下地処理剤のコスト
従来の溶剤系の下地処理剤と比較したコスト。（従来の溶剤系の下地処理剤のコストを１００とする）
３点：同等もしくは安い（１００以下）
２点：やや高い（１００を超え、１５０未満）
１点：高い（１５０以上）
（４）下地処理剤の浸透性
下地処理剤を無機質基材表面に塗装後、１０分経過後の無機質基材表面の塗装残りを目視にて評価した。
【００７６】
３点：塗装後短時間で浸透し、塗装残りなし
２点：塗装残りなし
１点：浸透不充分で塗装残りあり
（５）塗膜付き無機質基材の耐温水性試験
ＪＩＳ Ｋ ５４００ 8.19 に従い、塗膜付き無機質基材を５０℃の温水に１０日間浸漬させた後、引き上げ、乾燥させ、外観および密着性を評価した。
【００７７】
３点：外観異常なく、密着性は良好
２点：外観異常はないが、やや密着性不良
１点：外観異常（ブリスター）があり、密着性も不良
また、実施例、比較例で用いた成分は、次の通りである。
１．下地処理剤
・下地処理剤Ａ：
ＳＢＵイソシアネートＪ２４３〔商品名：住化バイエルウレタン（株）製、ＭＤＩイソシアヌレート体、２５ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
・下地処理剤Ｂ：
ＳＢＵイソシアネートＧ４０４Ｒ〔商品名：住化バイエルウレタン（株）製、ＭＤＩイソシアヌレート体、５０ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
・下地処理剤Ｃ：
ＬＤＩ〔商品名：協和発酵（株）製、リジンジイソシアネート（上記式（Ｉ）中、Ｒ1がメチル基）、１１ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
・下地処理剤Ｄ：
ＬＴＩ〔商品名：協和発酵（株）製、リジントリイソシアネート（上記式（II）中、Ｒ2がエチレン基）、２５ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
・下地処理剤Ｅ：
タケネートＤ−１７８Ｎ〔三井武田ケミカル（株）製、ＨＤＩアロファネート体、１１０ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
・下地処理剤Ｆ：
コロネートＨＸ〔商品名：日本ポリウレタン工業（株）製、ＨＤＩイソシアヌレート体〕５０％キシレン希釈品、５０ｍＰａ・ｓ（２５℃）
樹脂５０重量％、不揮発分５０％
・下地処理剤Ｇ：
ミリオネートＭＲ−２００〔商品名：日本ポリウレタン工業（株）製、変性ＭＤＩ、２００ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
・下地処理剤Ｈ：
スミジュール４４Ｖ−４０〔商品名：商品名：住化バイエルウレタン（株）製、変性ＭＤＩ、４００ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
・下地処理剤Ｉ：
コロネートＴ−８０〔商品名：日本ポリウレタン工業（株）製、ＴＤＩモノマー、３ｍＰａ・ｓ（２５℃）〕
樹脂１００重量％、不揮発分１００％
２．下塗り塗料組成物
ＥＰコートＮｏ．３００−３０（商品名；中国塗料（株）製、二液型アクルリルウレタン樹脂塗料）
３．上塗り塗料組成物
オーレックスＮｏ．２３０（商品名；中国塗料（株）製、紫外線硬化型ウレタンアクリレート樹脂塗料）
【００７８】
【実施例１】
珪酸カルシウム板を熱風乾燥機で板面温度を４０〜５０℃にプレヒートし、この板面に下地処理剤Ａをスポンジロールコーターを用い４５g/ｍ2の量で塗布し、さらに、８０℃の熱風で１５分間乾燥して下地処理膜付き珪酸カルシウム板を得た。
【００７９】
このようにして得られた下地処理膜付き珪酸カルシウム板に、上記の下塗り塗料組成物を、フローコーターにより１５０ｇ/ｍ2の量で塗布し、８０℃の熱風で２０分間乾燥して下塗り塗装板を得た。さらにこの下塗り塗装板に、上記の上塗塗料組成物を、フローコーターにより９０ｇ/ｍ2の量で塗布し、８０Ｗ／ｃｍ高圧水銀ランプを２灯を移動速度３ｍ／分で照射し、紫外線硬化させ、上塗り塗装板（塗膜付き無機質基材）を得た。
【００８０】
また、珪酸カルシウム板に代えて、フレキ板（石綿スレート板）を用い、下地処理剤Ａの塗布量を２０g/ｍ2とした以外は、上記と同様にして 、上塗り塗装板（塗膜付き無機質基材）を得た。
【００８１】
この下地処理剤の粘度、皮膚刺激性および浸透性、塗膜付き無機質基材の耐温水性試験の結果を表１に示す。
【００８２】
【実施例２〜５】
下地処理剤Ａに代えて下地処理剤Ｂ，Ｃ，Ｄ，Ｅを用いた以外は、実施例１と同様にして、上塗り塗装板（塗膜付き無機質基材）を得た。順に実施例２，３，４，５とする。
【００８３】
この下地処理剤の粘度、皮膚刺激性および浸透性、塗膜付き無機質基材の耐温水性試験の結果を表１に示す。
【００８４】
【比較例１〜４】
下地処理剤Ａに代えて下地処理剤Ｆ，Ｇ，Ｈ，Ｉを用いた以外は、実施例１と同様にして、上塗り塗装板（塗膜付き無機質基材）を得た。順に比較例１，２，３，４とする。
【００８５】
この下地処理剤の粘度、皮膚刺激性および浸透性、塗膜付き無機質基材の耐温水性試験の結果を表２に示す。
【００８６】
【表１】
【表２】
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a solvent-free surface treatment agent for an inorganic substrate and a method for treating a substrate of an inorganic substrate using the treatment agent.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Conventionally, inorganic base materials have been widely used for interior and exterior, roofs and the like as non-combustible building material plates. However, since the material of the inorganic base material is alkaline, there is a possibility that an alkali component oozes out [white flower (eflorescence)] on the surface of the base material, and it is necessary to prevent this. Furthermore, it is necessary to prevent the base material surface from being pulverized and to solidify and strengthen the brittle portion. Therefore, when coating the surface of an inorganic base material, generally, the surface is first coated with a sealer, and then a top coat is applied for the purpose of aesthetic appearance or the like.
[0003]
Conventionally, the above-described sealant coating of an inorganic base material is performed by performing an undercoat coating after performing an impregnation sealer coating (primary treatment) on the surface of the base material. Specifically, the sealer coating of such an inorganic base material first involves an isocyanate solution or epoxy diluted with a large amount of solvent on the surface of the inorganic base material in order to firmly adhere the sealer coating and the inorganic base material. This is done by applying the resin solution as an impregnating sealer (base treatment agent) and then applying an undercoating paint that conceals the substrate.
[0004]
In addition, as a sealer coating for other inorganic base materials, a solvent-based room temperature curing (reaction) type resin paint, for example, a two-component acrylic urethane resin paint is applied to the inorganic base material, and impregnation sealer coating and undercoat coating are performed in one step. (See, for example, Patent Document 1).
[0005]
However, in recent years, there are concerns about environmental pollution such as air pollution, water pollution, and soil pollution due to organic solvents, and effects on the human body. Compositions have been sought.
[0006]
In order to solve such a problem, an inorganic base material surface treatment method using a water-based surface treatment agent in which an emulsifiable hydrophilic group-containing isocyanate prepolymer is diluted in a large amount of water has been proposed (for example, Patent Documents). 2).
[0007]
However, since the base treatment film formed from such an emulsifying hydrophilic group-containing isocyanate prepolymer has a high affinity with water, the inorganic base material subjected to the pretreatment with this prepolymer has water resistance and warm water resistance. There was room for improvement.
[0008]
In addition, since the density of the inorganic base material varies depending on the type, the base treatment agent may not be allowed to penetrate to a desired depth. In such a case, water resistance, hot water resistance, etc. may become insufficient depending on the density of the inorganic substrate subjected to the ground treatment.
[0009]
[Patent Document 1]
Japanese Patent No. 2808399 [Patent Document 2]
JP-A-6-92756 gazette
OBJECT OF THE INVENTION
The present invention is intended to solve the problems associated with the prior art as described above, has high workability and safety in painting work, excellent in permeability and adhesion to various inorganic substrates, Furthermore, the present invention provides a solvent-free surface treatment agent for an inorganic base material that can form a surface treatment film excellent in water resistance, warm water resistance, and the like, and an inorganic substrate surface treatment method using the treatment agent. It is an object.
[0011]
SUMMARY OF THE INVENTION
(1) A solvent-free base material for inorganic base material comprising an isocyanate compound having a viscosity of 150 mPa · s (25 ° C.) or less.
(2) The surface treatment agent according to (1), wherein the isocyanate compound is lysine diisocyanate or lysine triisocyanate.
(3) The surface treatment agent according to (1), wherein the isocyanate compound is polyisocyanate obtained from hexamethylene diisocyanate or diphenylmethane diisocyanate or a prepolymer thereof.
(4) A base treatment film formed from the base treatment agent for an inorganic substrate according to any one of (1) to (3).
(5) A method for grounding an inorganic base material, wherein the surface of the inorganic base material is ground-treated with the ground base material treating agent for an inorganic base material according to any one of (1) to (3).
(6) The surface of the inorganic base material is ground-treated with the ground base material treating agent for inorganic base material according to any one of (1) to (3), and the surface of the base-treated film formed by the treatment is undercoated. A method for coating an inorganic base material, characterized in that
(7) The inorganic base material coating method according to (6), wherein the surface of the undercoat layer formed by the undercoat coating is patterned.
(8) The method for coating an inorganic base material according to (6), wherein the surface of the undercoat layer formed by the undercoat coating is overcoated.
(9) The method for coating an inorganic base material according to (7), wherein a top coat is applied to the surface of the patterned undercoat layer obtained by applying the pattern.
(10) The inorganic group according to (8) or (9), wherein the coating composition used for the top coating is an acrylic coating composition, an epoxy coating composition, or a urethane coating composition How to paint the material.
(11) The method for coating an inorganic base material according to (8) or (9), wherein the coating composition used for the top coating is an ultraviolet curable coating composition.
(12) An inorganic base material with a base treatment film manufactured by the base treatment method for an inorganic base material according to (5).
(13) An inorganic substrate with a coating film produced by the method according to any one of (6) to (11).
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
[0013]
First, a solventless inorganic base material treating agent (hereinafter, also simply referred to as “inorganic base material treating agent”) according to the present invention will be described.
[0014]
Solvent-free inorganic base material surface treatment agent The inorganic solvent-based ground material treatment agent according to the present invention comprises:
It is an undercoat agent composed of an isocyanate compound having a viscosity of 150 mPa · s (25 ° C.) or less and substantially free of an organic solvent or water. Since this surface treatment agent does not substantially contain an organic solvent, safety in coating work is high.
[0015]
Hereafter, the said component is demonstrated.
[0016]
Isocyanate compound The isocyanate compound used in the present invention has a viscosity (25 ° C) of 150 mPa · s or less, preferably 50 mPa · s or less, more preferably 10 to 25 mPa · s. The viscosity was measured using a B-type viscometer at a liquid temperature of 25 ° C.
[0017]
When the viscosity is in such a range, the obtained solvent-free base material for inorganic base material can be penetrated to a desired depth regardless of the type of the inorganic base material. That is, the solventless inorganic base material treating agent of the present invention can sufficiently permeate inorganic base materials having different densities. Therefore, the said base-treatment agent of this invention can fully provide water resistance, warm water resistance, etc. to various inorganic base materials.
[0018]
It is desirable that isocyanate groups remain in an amount of 20 to 50% by weight, preferably 30 to 40% by weight, in 100% by weight of the isocyanate compound. When the remaining isocyanate group is within the above range, the adhesive property between the coating film made of a solvent-free inorganic base material and the inorganic base material is excellent, and the water resistance and warm water resistance of the coating film are improved. Therefore, it is preferable.
[0019]
Examples of the isocyanate compound used in the present invention include isocyanate monomers such as diisocyanate and triisocyanate, polyisocyanate obtained from this isocyanate monomer, or a prepolymer thereof.
[0020]
Specific examples of the diisocyanate include aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate [MDI] and xylylene diisocyanate [XDI];
Cycloaliphatic diisocyanates such as methylenebis (4-cyclohexylisocyanate) [HMDI], isophorone diisocyanate [IPDI];
Examples include aliphatic diisocyanates such as hexamethylene diisocyanate [HDI], trimethylhexamethylene diisocyanate [TMHMDI], and lysine diisocyanate (LDI).
[0021]
Specific examples of the triisocyanate include triphenylmethane triisocyanate and lysine triisocyanate (LTI).
[0022]
The diisocyanate or triisocyanate is not particularly limited as long as it is in the above viscosity range, but lysine diisocyanate (LDI) represented by the following formula (I) and lysine triisocyanate (LTI) represented by the following formula (II) are preferable.
[0023]
Such a base treatment agent for an inorganic base material using LDI and LTI adheres firmly to the inorganic base material, and can form a base treatment film with improved water resistance and warm water resistance.
[0024]
[Chemical 1]
In the above formula (I), R 1 is preferably an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
[0026]
[Chemical 2]
In the above formula (II), R 2 is desirably an alkylene group having 2 to 8 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably ethylene. The alkylene group may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms, a phenyl group, or the like.
[0028]
In addition, the polyisocyanate or prepolymer thereof used in the present invention is an isocyanurate body having an isocyanurate ring represented by the following formula (III) obtained from the diisocyanate or triisocyanate, a burette body, a trimethylolpropane adduct. Body, allophanate body and the like.
[0029]
[Chemical 3]
The polyisocyanate or the prepolymer thereof is not particularly limited as long as it is in the above viscosity range.
[0031]
Such a base treatment agent for an inorganic base material using a polyisocyanate or a prepolymer thereof can adhere firmly to the inorganic base material, and can form a base treatment film with improved water resistance and warm water resistance.
[0032]
Specific examples of the isocyanate compound used in the present invention include LDI [trade name: manufactured by Kyowa Hakko Co., Ltd., lysine diisocyanate (in the above formula (I) , R 1 is a methyl group), 11 mPa · s (25 ° C. ), Number average molecular weight 212], LTI [trade name: manufactured by Kyowa Hakko Co., Ltd., lysine triisocyanate (in the above formula (II) , R 2 is an ethylene group), 25 mPa · s (25 ° C.), number average molecular weight 267 ], SBU isocyanate J243 (trade name: manufactured by Sumika Bayer Urethane Co., Ltd., modified MDI, 25 mPa · s (25 ° C), number average molecular weight 390), SBU isocyanate G404R (trade name: manufactured by Sumika Bayer Urethane Co., Ltd.) , Modified MDI, 50 mPa · s (25 ° C., number average molecular weight 400), Takenate D-178N (manufactured by Mitsui Takeda Chemical Co., Ltd., HDI alof) Sulfonates body, 110mPa · s (25 ℃), the number average molecular weight 450), and the like.
[0033]
The above isocyanate compounds can be used alone or in combination of two or more.
[0034]
Other Components The solventless inorganic base material treating agent of the present invention basically comprises an isocyanate compound within the above viscosity range .
[0037]
Specifically, the above-mentioned isocyanate compound can be added at a predetermined ratio once or in any order, and stirred, mixed, and uniformly dissolved / dispersed to prepare a base treatment agent for an inorganic substrate.
[0038]
A method for treating the base material of the inorganic base material using such a solvent-free base material for inorganic base material will be described below.
[0039]
Inorganic substrate substrate treatment method The inorganic substrate substrate treatment method of the present invention is carried out on the surface of an inorganic substrate preheated with a hot air dryer or the like so as to have a temperature of about 40 to 60C. This is performed by applying a base treatment agent for an inorganic base material to form a base treatment film.
[0040]
Examples of the inorganic base material include a flexible board (asbestos slate board), a fiber cement board, a calcium silicate board, a gypsum board, a concrete board, and the like, and the surface shape may be flat or uneven. Moreover, as a coating method, the method of apply | coating with coating machines, such as a spray, a flow coater, a roll coater, etc. is mentioned.
[0041]
The processing amount of the solvent-free inorganic base material treatment agent varies depending on the density of the base material, but is preferably 30 to 60 g / m 2 , and preferably 40 to 50 g / m 2 .
If it is less than 30 g / m 2 , the adhesion between the base treatment film and the inorganic base material is weak, and if it exceeds 60 g / m 2 , the base treatment film is slow to cure and there is a problem in workability.
[0042]
After coating as described above, using a hot air dryer or the like, it is dried at about 60 to 80 ° C. for about 10 to 20 minutes to form a base treatment film on the surface of the inorganic substrate.
[0043]
In the present invention, it is only necessary that the surface treatment agent of the present invention is impregnated to a desired depth in the inorganic base material, and the thickness of the ground surface treatment film after drying formed on the surface of the inorganic base material is not particularly limited. The thickness is usually 20 to 50 μm (thickness), preferably 30 to 40 μm (thickness). With such a film thickness, a ground treatment film excellent in water resistance, warm water resistance and the like can be obtained.
[0044]
This inorganic base material surface treatment agent contains the aforementioned isocyanate compound. Therefore, when the isocyanate group of the isocyanate compound forms a urethane bond with the hydroxyl group on the surface of the inorganic base material and further the moisture in the inorganic base material, the base treatment film obtained from this composition and the inorganic base material adhere firmly. Conceivable.
[0045]
Since the ground treatment method of the inorganic base material of the present invention uses the above ground treatment agent, the workability and safety in the painting work are high, and the permeability and adhesion to various inorganic base materials are excellent. It is possible to form a base treatment film having excellent properties and hot water resistance.
[0046]
In the present invention, the inorganic base material with a base treatment film thus obtained is further coated. The coating method of this inorganic base material is demonstrated below.
[0047]
Method for coating inorganic base material The method for coating an inorganic base material of the present invention comprises subjecting the surface of the inorganic base material to a base treatment as described above, and then applying a primer coating to the surface of the formed base treatment film. Furthermore, it is a coating method in which a top coat is applied to the surface of the formed undercoat layer.
[0048]
First, the undercoating will be described below.
[0049]
(Undercoating)
The primer coating composition used for the primer coating is acrylic resin coating composition, acrylic-urethane resin coating composition, acrylic silicone resin coating composition, vinyl acetate resin coating composition, urethane resin coating composition, epoxy resin coating composition. Conventionally known coating compositions such as products and alkyd resin coating compositions can be used.
These undercoat paint compositions may be either solvent-based paint compositions or water-based paint compositions.
[0050]
Such an undercoating composition may contain a coloring pigment, an extender pigment, a filler, an antiseptic, an antifungal agent, a weathering stabilizer, a matting material such as silica, an aggregate, and the like together with these resins. good. Examples of the aggregate include mica, cinnabar, glass beads, and colored products thereof.
[0051]
In the present invention, the undercoating composition preferably contains the resin component, a color pigment, and the like.
[0052]
Examples of the coating method of the undercoat coating composition include a method of applying with a coating machine such as a spray, a flow coater, a roll coater or the like. After applying the undercoat coating composition as described above, it can be dried and cured by hot air drying, ultraviolet irradiation, electron beam irradiation or the like by a conventionally known method to form an undercoat layer on the surface of the base treatment film.
[0053]
The dry film thickness of such an undercoat layer is not particularly limited, but is usually about 40 to 70 μm, preferably about 50 to 60 μm.
[0054]
By applying such an undercoat coating composition so as to have the above-mentioned film thickness, it has excellent adhesion to the base treatment film, can conceal the surface of the inorganic base material, has excellent weather resistance, and is also applied to the surface of the inorganic base material. It is possible to easily grasp the application state of the paint.
[0055]
Further, in the present invention, it is preferable to perform undercoating as described above on the surface of the film made of a solvent-free inorganic base material surface treating agent, and further patterning the surface of the undercoating layer.
[0056]
Examples of the patterning method include various patterning methods such as screen printing, letterpress printing, flexographic printing, flat plate printing, gravure printing, and thermal transfer. Such patterning is performed by a conventionally known method.
[0057]
In the present invention, an electron beam curable undercoating composition may be used as the undercoating composition, and the curing of the undercoating layer and the printing step may be performed simultaneously (one step).
[0058]
In this manner, an undercoat layer (preferably, an undercoat layer whose surface is patterned) is further formed on the surface of the base treatment film obtained by the above-described inorganic base material base treatment method. In the method for coating an inorganic base material of the present invention, the surface of the undercoat layer is further overcoated to form an overcoat layer.
[0059]
Hereinafter, the top coating will be described.
[0060]
(Top coating)
As the top coat composition (for example, clear paint, color clear paint) used in this top coat, either a solvent-based paint composition or a water-based paint composition can be used, and it is appropriately selected according to the undercoat paint composition. The
[0061]
The solvent-based coating composition includes an acrylic resin coating composition, an epoxy resin coating composition, a urethane resin coating composition, a phenol resin coating composition, a fluororesin coating composition, and a silicone resin from the viewpoints of alkali resistance and weather resistance. Synthetic resin coating compositions such as coating compositions and acrylic silicone resin coating compositions can be used.
[0062]
Examples of the water-based paint composition include an acrylic resin paint composition, a vinyl acetate paint composition, a styrene resin paint composition, a urethane resin paint composition, a silicone resin paint composition, an acrylic silicone resin paint composition, and an epoxy resin paint. A synthetic resin emulsion-based coating composition such as a composition or a fluororesin coating composition can be used.
[0063]
In addition to these resins, such top coating compositions contain coloring pigments, extender pigments, fillers, antibacterial agents, antiseptics, antifungal agents, weathering stabilizers, matte materials such as silica, aggregates, and the like. May be.
As the top coating composition used in the present invention, an acrylic coating composition, an epoxy coating composition or a urethane coating composition is preferably used. By using these coating compositions, good surface performance such as stain resistance and chemical resistance can be obtained.
[0064]
Further, the top coating composition used in the present invention is preferably a photocurable coating composition. Examples of the photo-curable coating composition include polyester (meth) acrylate resin coating composition, epoxy (meth) acrylate resin coating composition, polyether (meth) acrylate resin coating composition, polyurethane (meth) acrylate resin coating composition. A thing etc. can be used. Such a photocurable coating composition is preferable because it has a high curing rate and excellent workability.
[0065]
Using such a top coating composition, a top coating is applied to the surface of the undercoat layer by line coating, on-site construction, or the like. In this line painting method, a spray, a flow coater, a roll coater or the like can be used. In the on-site construction, the undercoating plate may be constructed on-site, and then a top coat may be applied.
[0066]
After applying the top coating composition as described above, it is dried and cured by hot air drying, ultraviolet irradiation or the like by a conventionally known method to form a top coating layer on the surface of the undercoat layer, and the coated inorganic substrate of the present invention Can be manufactured.
[0067]
The film thickness of this overcoat layer (cured film) is usually about 40 to 80 μm (thickness), preferably about 60 to 70 μm (thickness). Thus, by apply | coating a top-coat coating composition so that it may become said film thickness, it is excellent in adhesiveness with an undercoat layer, and can obtain the inorganic base material with a coating film which is excellent in a weather resistance and water resistance.
[0068]
Moreover, although the aspect which forms a topcoat layer in the undercoat layer surface in this invention was demonstrated, the intermediate coat film may be formed between the undercoat layer and the topcoat layer.
[0069]
The inorganic base material with a coating film obtained in this way is excellent in terms of the so-called “finish” because the surface-free surface treatment agent for inorganic base material is used and the surface becomes very smooth. It becomes. Furthermore, the inorganic substrate with a coating film of the present invention is excellent in water resistance and warm water resistance, and is excellent in adhesion to the substrate surface. Therefore, the inorganic base material with a coating film of the present invention can be used for interior and exterior, roofs, and the like, and is particularly suitably used for building materials around water such as bathrooms, washrooms, kitchens and the like.
[0070]
【The invention's effect】
According to the present invention, the workability and safety in the painting work are high, and the base treatment film is excellent in permeability and adhesion to various inorganic substrates, and further in water resistance, warm water resistance and the like. It is possible to provide a non-solvent base treatment agent for an inorganic substrate and a method for treating an inorganic substrate using the treatment agent.
[0071]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[0072]
In the following examples and comparative examples, “parts” means all parts by weight.
[0073]
In addition, the solvent-free base material for inorganic base materials and the inorganic base material with a coating film obtained in Examples and Comparative Examples were evaluated according to the following criteria.
[0074]
(1) Viscosity of the surface treatment agent Measurement conditions: B-type viscometer, liquid temperature 25C
(2) Skin irritation of the surface treatment agent 0.5 ml of the surface treatment agent was attached to the rabbit skin (25 mm x 25 mm), and the skin irritation after 24 hours was visually observed according to the following criteria. And evaluated.
[0075]
3 points: weakly irritating 2 points: slightly irritating 1 point: strongly irritating
(3) Cost of surface treatment agent Cost compared with conventional solvent-based surface treatment agent. (The cost of the conventional solvent-based surface treatment agent is 100)
3 points: Equivalent or cheap (100 or less)
2 points: Slightly high (above 100 and less than 150)
1 point: high (over 150)
(4) Penetration of the base treatment agent After coating the base treatment agent on the surface of the inorganic base material, the coating residue on the surface of the inorganic base material after 10 minutes was visually evaluated.
[0076]
3 points: Penetration in a short time after painting, no paint residue 2 points: no paint residue 1 point: insufficient penetration and paint residue
(5) Warm water resistance test of inorganic base material with coating film In accordance with JIS K 5400 8.19, the inorganic base material with coating film was immersed in warm water at 50 ° C. for 10 days, then lifted and dried, and the appearance and adhesion were evaluated. did.
[0077]
3 points: no appearance abnormality, good adhesion 2 points: no appearance abnormality, but slightly poor adhesion 1 point: appearance abnormality (blister), poor adhesion Also, components used in Examples and Comparative Examples Is as follows.
1. Surface treatment agent / surface treatment agent A:
SBU isocyanate J243 [trade name: manufactured by Sumika Bayer Urethane Co., Ltd., MDI isocyanurate, 25 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
-Ground treatment agent B:
SBU isocyanate G404R [trade name: Sumika Bayer Urethane Co., Ltd., MDI isocyanurate, 50 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
-Ground treatment agent C:
LDI [trade name: manufactured by Kyowa Hakko Co., Ltd., lysine diisocyanate (in the above formula (I), R 1 is a methyl group), 11 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
-Ground treatment agent D:
LTI [trade name: manufactured by Kyowa Hakko Co., Ltd., lysine triisocyanate (in the above formula (II), R 2 is an ethylene group), 25 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
-Ground treatment agent E:
Takenate D-178N [manufactured by Mitsui Takeda Chemical Co., Ltd., HDI allophanate, 110 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
-Ground treatment agent F:
Coronate HX [trade name: manufactured by Nippon Polyurethane Industry Co., Ltd., HDI isocyanurate] 50% xylene diluted product, 50 mPa · s (25 ° C.)
50% resin, 50% non-volatile content
・ Ground treatment agent G:
Millionate MR-200 [trade name: manufactured by Nippon Polyurethane Industry Co., Ltd., modified MDI, 200 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
-Ground treatment agent H:
Sumidur 44V-40 [trade name: trade name: manufactured by Sumika Bayer Urethane Co., Ltd., modified MDI, 400 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
-Ground treatment agent I:
Coronate T-80 [trade name: manufactured by Nippon Polyurethane Industry Co., Ltd., TDI monomer, 3 mPa · s (25 ° C.)]
Resin 100% by weight, nonvolatile content 100%
2. Undercoat paint composition EP coat No. 300-30 (Brand name; China Paint Co., Ltd., two-pack type acrylyl urethane resin paint)
3. Top coating composition Aurex No. 230 (trade name; manufactured by China Paint Co., Ltd., UV curable urethane acrylate resin paint)
[0078]
[Example 1]
A calcium silicate plate is preheated to a temperature of 40 to 50 ° C. with a hot air dryer, and the surface treatment agent A is applied to the plate surface in an amount of 45 g / m 2 using a sponge roll coater, and further hot air at 80 ° C. And dried for 15 minutes to obtain a calcium silicate plate with a base treatment film.
[0079]
The undercoating composition is applied to the calcium silicate plate with the base treatment film obtained in this manner in an amount of 150 g / m 2 by a flow coater and dried with hot air at 80 ° C. for 20 minutes to form an undercoating plate. Got. Furthermore, the above-mentioned top coat composition is applied to this undercoat plate by a flow coater in an amount of 90 g / m 2 , and two 80 W / cm high-pressure mercury lamps are irradiated at a moving speed of 3 m / min to be cured by ultraviolet rays. A top-coated plate (inorganic substrate with a coating film) was obtained.
[0080]
In addition, a top-coated board (inorganic with coating film) was used in the same manner as above except that a flexible board (asbestos slate board) was used instead of the calcium silicate board and the coating amount of the base treatment agent A was 20 g / m 2. Substrate) was obtained.
[0081]
Table 1 shows the viscosity, skin irritation and permeability, and the results of the warm water resistance test of the coated inorganic base material.
[0082]
[Examples 2 to 5]
A top coat plate (an inorganic substrate with a coating film) was obtained in the same manner as in Example 1 except that the base treatment agents B, C, D, and E were used in place of the base treatment agent A. It is set as Example 2, 3, 4, 5 in order.
[0083]
Table 1 shows the viscosity, skin irritation and permeability, and the results of the warm water resistance test of the coated inorganic base material.
[0084]
[Comparative Examples 1-4]
A top coat plate (inorganic substrate with a coating film) was obtained in the same manner as in Example 1 except that the base treatment agents F, G, H, and I were used in place of the base treatment agent A. These are referred to as Comparative Examples 1, 2, 3, and 4 in order.
[0085]
Table 2 shows the viscosity, skin irritation and permeability, and the results of the warm water resistance test of the coated inorganic base material.
[0086]
[Table 1]
[Table 2]
Claims (15)
（１）ヘキサメチレンジイソシアネートから得られる、ポリイソシアネートまたはそのプレポリマー
（２）ジフェニルメタンジイソシアネートから得られる、ポリイソシアネートまたはそのプレポリマー
（３）リジンジイソシアネートFollowing (1) to a differentially alone (one) or two or more isocyanate compounds selected from (3), that the viscosity of the body of the isocyanate compound is 10~25mPa · s (25 ℃) A solvent-free surface treatment agent for inorganic substrates.
(1) Polyisocyanate or its prepolymer obtained from hexamethylene diisocyanate (2) Polyisocyanate or its prepolymer obtained from diphenylmethane diisocyanate (3) Lysine diisocyanate
（１）ヘキサメチレンジイソシアネートまたはジフェニルメタンジイソシアネートから得られる、ポリイソシアネートまたはそのプレポリマー
（２）リジンジイソシアネートFollowing (1) or (2) solvent-free inorganic substrate for ground processing material viscosity is characterized in that it consists only isocyanate Monotan Germany is 10~25mPa · s (25 ℃) selected from.
(1) Polyisocyanate or prepolymer thereof obtained from hexamethylene diisocyanate or diphenylmethane diisocyanate (2) Lysine diisocyanate
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| JP4697469B2 (en) * | 2007-02-02 | 2011-06-08 | 亜細亜工業株式会社 | Primer composition and method for producing the same |
| JP5083947B2 (en) * | 2007-05-12 | 2012-11-28 | コニシ株式会社 | Impregnated sealer for application to siliceous inorganic porous materials |
| CN110337366A (en) * | 2017-02-24 | 2019-10-15 | 爱克工业株式会社 | Ornament materials and its manufacturing method |
| JP7084734B2 (en) * | 2018-01-31 | 2022-06-15 | 旭化成株式会社 | How to impart blocking resistance to the adherend |
| JP7365128B2 (en) * | 2019-03-08 | 2023-10-19 | 株式会社エーアンドエーマテリアル | Ceramic decorative board |
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|---|---|---|---|---|
| JP2000043215A (en) * | 1998-07-29 | 2000-02-15 | Daiken Trade & Ind Co Ltd | Production of inorganic decorative panel |
| JP2002308961A (en) * | 2001-04-13 | 2002-10-23 | Asia Kogyo Kk | Moisture-curing resin composition and sealer for inorganic material |
| JP2003292929A (en) * | 2002-04-03 | 2003-10-15 | Asahi Kasei Corp | Adhesive and primer |
| JP2003327904A (en) * | 2002-05-13 | 2003-11-19 | Nippon Polyurethane Ind Co Ltd | Primer for porous base and method for carrying out primer treatment of porous base |
| JP2004035717A (en) * | 2002-07-03 | 2004-02-05 | Chugoku Marine Paints Ltd | Ground-treating composition for inorganic base material, and method for treating ground of inorganic base material by using the composition |
| JP2004196914A (en) * | 2002-12-17 | 2004-07-15 | Chugoku Marine Paints Ltd | Aqueous sealer composition for inorganic base material, and method for preparing surface of inorganic base material using the same |
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|---|---|---|---|---|
| JPS4820606B1 (en) * | 1970-05-18 | 1973-06-22 | ||
| JPS53137234A (en) * | 1977-05-07 | 1978-11-30 | Chugoku Marine Paints | Intermediate coating composition |
| DE3042821A1 (en) * | 1980-11-13 | 1982-06-09 | Bayer Ag, 5090 Leverkusen | METHOD FOR SEALING CONSTRUCTIONS |
| JPS60232277A (en) * | 1985-03-12 | 1985-11-18 | Mitsubishi Heavy Ind Ltd | Method for painting inferior material |
| JPH09324167A (en) * | 1996-06-04 | 1997-12-16 | Yokohama Rubber Co Ltd:The | Solventless type primer composition |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000043215A (en) * | 1998-07-29 | 2000-02-15 | Daiken Trade & Ind Co Ltd | Production of inorganic decorative panel |
| JP2002308961A (en) * | 2001-04-13 | 2002-10-23 | Asia Kogyo Kk | Moisture-curing resin composition and sealer for inorganic material |
| JP2003292929A (en) * | 2002-04-03 | 2003-10-15 | Asahi Kasei Corp | Adhesive and primer |
| JP2003327904A (en) * | 2002-05-13 | 2003-11-19 | Nippon Polyurethane Ind Co Ltd | Primer for porous base and method for carrying out primer treatment of porous base |
| JP2004035717A (en) * | 2002-07-03 | 2004-02-05 | Chugoku Marine Paints Ltd | Ground-treating composition for inorganic base material, and method for treating ground of inorganic base material by using the composition |
| JP2004196914A (en) * | 2002-12-17 | 2004-07-15 | Chugoku Marine Paints Ltd | Aqueous sealer composition for inorganic base material, and method for preparing surface of inorganic base material using the same |
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