JP4862976B2 - Green pigment, paint and resin composition using the green pigment - Google Patents

Description

【００３３】
アルコキシシランとしては、具体的には、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、ジメチルジメトキシシラン、メチルトリメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、イソブチルトリメトキシシラン、デシルトリメトキシシラン等が挙げられる。
【００３４】
有機青色顔料の付着効果及び脱離率を考慮すると、メチルトリエトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、イソブチルトリメトキシシラン、フェニルトリエトキシシランから生成するオルガノシラン化合物が好ましく、メチルトリエトキシシラン、メチルトリメトキシシランから生成するオルガノシラン化合物がより好ましい。
【００３５】
本発明におけるポリシロキサンは、化２で表わされるポリシロキサン、化３で表わされる変成ポリシロキサン、化４で表わされる末端変成ポリシロキサン又はこれらの混合物を用いることができる。
【００３６】
【化２】

【００３７】
【化３】

【００３８】
【化４】

【００３９】
有機青色顔料の付着効果及び脱離率を考慮すると、メチルハイドロジェンシロキサン単位を有するポリシロキサン、ポリエーテル変成ポリシロキサン及び末端がカルボン酸で変成された末端カルボン酸変成ポリシロキサンが好ましい。
【００４０】
オルガノシラン化合物又はポリシロキサンの被覆量は、オルガノシラン化合物被覆含水酸化鉄粒子粉末、又は、ポリシロキサン被覆含水酸化鉄粒子粉末に対して、Ｓｉ換算で０．０２〜５．０重量％であることが好ましく、より好ましくは０．０３〜４．０重量％であり、更により好ましくは０．０５〜３．０重量％である。
【００４１】
０．０２重量％未満の場合には、含水酸化鉄粒子粉末１００重量部に対して５重量部以上の有機青色顔料を付着させることが困難である。
【００４２】
５．０重量％を超える場合には、含水酸化鉄粒子粉末１００重量部に対して有機青色顔料を５〜３０重量部付着させることができるため、必要以上に被覆する意味がない。
【００４３】
本発明における有機青色顔料は、フタロシアニンブルー、無金属フタロシアニンブルー、ファストスカイブルー等のフタロシアニン系顔料及びアルカリブルーであり、得られる緑色系顔料の耐薬品性を考慮した場合、フタロシアニン系顔料を用いることが好ましい。
【００４４】
有機青色顔料の付着量は、含水酸化鉄粒子粉末１００重量部に対して５〜３０重量部である。
【００４５】
５重量部未満の場合及び３０重量部を超える場合には、本発明の目的とする緑色系顔料を得ることが困難となる。より好ましくは７．５〜２５重量部である。
【００４６】
本発明に係る緑色系顔料の粒子形状や粒子サイズは、芯粒子である含水酸化鉄粒子の粒子形状や粒子サイズに大きく依存し、芯粒子に相似する粒子形態を有している。
【００４７】
即ち、本発明に係る緑色系顔料は、平均長軸径が０．１〜１．０μｍ、好ましくは０．１５〜０．９μｍである。
【００４８】
緑色系顔料の平均長軸径が１．０μｍを超える場合には、粒子サイズが大きすぎるため、着色力が低下する。平均長軸径が０．１μｍ未満の場合には、粒子の微細化による分子間力の増大により凝集を起こしやすいため、ビヒクル中や樹脂組成物中への分散が困難となる。
【００４９】
本発明に係る緑色系顔料の形状は、針状又は直方体状である。
【００５０】
本発明に係る緑色系顔料の軸比は２０以下が好ましく、より好ましくは２〜１５、更により好ましくは２〜１０である。軸比が２０を超える場合には、粒子の絡み合いが多くなり、ビヒクル中や樹脂組成物中への分散性が悪くなったり粘度が増加する場合がある。
【００５１】
緑色系顔料の長軸径の幾何標準偏差値は、２．０以下であることが好ましい。２．０を超える場合には、存在する粗大粒子によってビヒクル中や樹脂組成物中への均一な分散が困難となる。ビヒクル中や樹脂組成物中への均一な分散を考慮すれば、好ましくは１．８以下、より好ましくは１．６以下である。工業的な生産性を考慮すれば、緑色系顔料の粒子径の幾何標準偏差値の下限値は１．０１であり、１．０１未満のものは工業的に得られ難い。
【００５２】
本発明に係る緑色系顔料のＢＥＴ比表面積値は６〜１６０ｍ^２／ｇが好ましく、より好ましくは１１〜１３０ｍ^２／ｇ、更により好ましくは１６〜１１０ｍ^２／ｇである。ＢＥＴ比表面積値が６ｍ^２／ｇ未満の場合には、緑色系顔料が粗大であるため、着色力が低下する。ＢＥＴ比表面積値が１６０ｍ^２／ｇを超える場合には、粒子の微細化による分子間力の増大により凝集を起こしやすいため、ビヒクル中や樹脂組成物中への分散性が低下する。
【００５３】
本発明に係る緑色系顔料の有機青色顔料の脱離率は１５％以下が好ましく、より好ましくは１２％以下である。有機青色顔料の脱離率が１５％を超える場合には、脱離した有機青色顔料によりビヒクル中や樹脂組成物中での均一な分散が阻害される場合があると共に、脱離した部分の含水酸化鉄粒子粉末の色相が複合含水酸化鉄粒子粉末の粒子表面に現れるため、均一な色相を得ることが困難となる。
【００５４】
本発明に係る緑色系顔料の色相は、Ｌ^＊値が２５〜８０、ａ^＊値が−１００≦ａ^＊値＜０、ｂ^＊値が−１００≦ｂ^＊値≦＋１００及びｈ値が１２０°≦ｈ値≦２４０°の範囲のものである。
【００５５】
本発明に係る緑色系顔料の耐熱性は、粒子粉末である含水酸化鉄粒子粉末の耐熱温度に対して＋５〜＋４０℃向上する。
【００５６】
本発明に係る緑色系顔料の着色力は、後出する評価方法で１１５％以上が好ましく、より好ましくは１２０％以上である。
【００５７】
本発明に係る緑色系顔料の隠蔽力は、後出する評価方法で１，７５０ｃｍ^２／ｇ以上が好ましく、より好ましくは１，８００ｃｍ^２／ｇ以上である。
【００５８】
本発明に係る緑色系顔料の耐薬品性は、後出する評価方法で、耐酸性はΔＥ^＊値が１．５以下が好ましく、より好ましくは１．２以下であり、耐アルカリ性はΔＥ^＊値が１．５以下が好ましく、より好ましくは１．２以下である。
【００５９】
本発明に係る緑色系顔料は、必要により、含水酸化鉄粒子粉末の粒子表面をあらかじめ、アルミニウムの水酸化物、アルミニウムの酸化物、ケイ素の水酸化物及びケイ素の酸化物より選ばれる少なくとも１種からなる中間被覆物で被覆しておいてもよく、中間被覆物で被覆しない場合に比べ、含水酸化鉄粒子粉末の粒子表面からの有機青色顔料の脱離をより低減することができると共に、若干、耐熱性が向上する。
【００６０】
中間被覆物による被覆量は、中間被覆物が被覆された含水酸化鉄粒子粉末に対してＡｌ換算、ＳｉＯ_２換算又はＡｌ換算量とＳｉＯ_２換算量との総和で０．０１〜２０重量％が好ましい。
【００６１】
０．０１重量％未満である場合には、有機青色顔料の脱離率の低減効果が得られない。０．０１〜２０重量％の被覆量により、有機青色顔料の脱離率低減効果が十分に得られるので、２０重量％を超えて必要以上に被覆する意味がない。
【００６２】
中間被覆物で被覆されている本発明に係る緑色系顔料は、中間被覆物で被覆されていない本発明に係る緑色系顔料の場合とほぼ同程度の粒子サイズ、幾何標準偏差値、ＢＥＴ比表面積値、色相（Ｌ^＊値、ａ^＊値、ｂ^＊値、ｈ値）、着色力、隠蔽力及び耐薬品性を有している。また、緑色系顔料の脱離率は中間被覆物を被覆することによって向上し、脱離率は１２％以下が好ましく、より好ましくは１０％以下である。また、耐熱性は、アルミニウムを含有していない芯粒子粉末を用いた緑色系顔料に対して＋５〜＋３０℃程度向上する。
【００６３】
次に、本発明に係る緑色系顔料を配合した塗料について述べる。
【００６４】
本発明に係る緑色系顔料を配合した塗料は、貯蔵安定性がΔＥ^＊値で１．５以下が好ましく、より好ましくは１．２以下である。塗膜にした場合には、光沢度は７５〜１１０％、好ましくは８０〜１１０％であり、塗膜の耐熱温度は２４０℃以上、好ましくは２４５℃以上であり、耐薬品性のうち耐酸性はΔＧ値で１２％以下が好ましく、より好ましくは１０％以下であり、耐アルカリ性はΔＧ値で１２％以下が好ましく、より好ましくは１０％以下であり、色相はＬ^＊値が２５〜８５、ａ^＊値が−１００≦ａ^＊値＜０、ｂ^＊値が−１００≦ｂ^＊値≦＋１００及びｈ値が１２０°≦ｈ値≦２４０°であることが好ましい。
【００６５】
本発明に係る粒子表面が中間被覆物によって被覆された緑色系顔料を配合した塗料は、貯蔵安定性がΔＥ^＊値で１．５以下が好ましく、より好ましくは１．２以下である。塗膜にした場合、光沢度は８０〜１１５％、好ましくは８５〜１１５％であり、塗膜の耐熱温度は２４５℃以上、好ましくは２５０℃以上であって、耐薬品性のうち耐酸性はΔＧ値で１２％以下が好ましく、より好ましくは１０％以下であり、耐アルカリ性はΔＧ値で１２％以下が好ましく、より好ましくは１０％以下であり、色相はＬ^＊値が２５〜８５、ａ^＊値が−１００≦ａ^＊値＜０、ｂ^＊値が−１００≦ｂ^＊値≦＋１００及びｈ値が１２０°≦ｈ値≦２４０°であることが好ましい。
【００６６】
本発明に係る緑色系顔料を配合した水系塗料は、貯蔵安定性がΔＥ^＊値で１．５以下が好ましく、より好ましくは１．２以下である。塗膜にした場合には、光沢度は７０〜１１０％、好ましくは７５〜１１０％であり、塗膜の耐熱温度は２３５℃以上、好ましくは２４０℃以上であり、耐薬品性のうち耐酸性はΔＧ値で１２％以下が好ましく、より好ましくは１０％以下であり、耐アルカリ性はΔＧ値で１２％以下が好ましく、より好ましくは１０％以下であり、色相はＬ^＊値が２５〜８５、ａ^＊値が−１００≦ａ^＊値＜０、ｂ^＊値が−１００≦ｂ^＊値≦＋１００及びｈ値が１２０°≦ｈ値≦２４０°であることが好ましい。
【００６７】
本発明に係る粒子表面が中間被覆物によって被覆された緑色系顔料を配合した水系塗料は、貯蔵安定性がΔＥで１．５以下が好ましく、より好ましくは１．２以下である。塗膜にした場合、光沢度は７５〜１１５％、好ましくは８０〜１１５％であり、塗膜の耐熱温度は２４０℃以上、好ましくは２４５℃以上であって、耐薬品性のうち耐酸性はΔＧ値では１２％以下が好ましく、より好ましくは１０％以下であり、耐アルカリ性はΔＧ値で１２％以下が好ましく、より好ましくは１０％以下であり、色相はＬ^＊値が２５〜８５、ａ^＊値が−１００≦ａ^＊値＜０、ｂ^＊値が−１００≦ｂ^＊値≦＋１００及びｈ値が１２０°≦ｈ値≦２４０°であることが好ましい。
【００６８】
本発明に係る塗料中における緑色系顔料の配合割合は、塗料構成基材１００重量部に対し１．０〜１００重量部の範囲で使用することができ、塗料のハンドリングを考慮すれば、好ましくは２．０〜１００重量部、更に好ましくは５．０〜１００重量部である。
【００６９】
塗料構成基材としては、樹脂、溶剤、必要により消泡剤、体質顔料、乾燥促進剤、界面活性剤、硬化促進剤、助剤等が配合される。
【００７０】
樹脂としては、溶剤系塗料用として通常使用されるアクリル樹脂、アルキッド樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、アミノ樹脂等を用いることができる。水系塗料用としては、通常使用される水溶性アルキッド樹脂、水溶性メラミン樹脂、水溶性アクリル樹脂、水溶性ウレタンエマルジョン樹脂等を用いることができる。
【００７１】
溶剤としては、溶剤系塗料用として通常使用されるトルエン、キシレン、ブチルアセテート、メチルアセテート、メチルイソブチルケトン、ブチルセロソルブ、エチルセロソルブ、ブチルアルコール、脂肪族炭化水素等を用いることができる。
【００７２】
水系塗料用溶剤としては、水と水系塗料で通常使用されるブチルセロソルブ、ブチルアルコール等とを混合して使用することができる。
【００７３】
消泡剤としては、ノプコ８０３４（商品名）、ＳＮデフォーマー４７７（商品名）、ＳＮデフォーマー５０１３（商品名）、ＳＮデフォーマー２４７（商品名）、ＳＮデフォーマー３８２（商品名）（以上、いずれもサンノプコ株式会社製）、アンチホーム０８（商品名）、エマルゲン９０３（商品名）（以上、いずれも花王株式会社製）等の市販品を使用することができる。
【００７４】
次に、本発明に係る緑色系顔料を用いて着色した樹脂組成物について述べる。
【００７５】
本発明に係る緑色系顔料を用いて着色した樹脂組成物は、目視観察による分散状態は、後出評価法による４又は５、好ましくは５であり、樹脂組成物の耐熱温度は２１５℃以上、好ましくは２２０℃以上であって、色相はＬ^＊値が２５〜８５、ａ^＊値が−１００≦ａ^＊値＜０、ｂ^＊値が−１００≦ｂ^＊値≦＋１００及びｈ値が１２０°≦ｈ値≦２４０°であることが好ましい。
【００７６】
本発明に係る粒子表面が中間被覆物によって被覆された緑色系顔料を用いて着色した樹脂組成物は、目視観察による分散状態は、後出評価法による４又は５、好ましくは５であり、樹脂組成物の耐熱温度は２２０℃以上、好ましくは２２５℃以上であって、色相はＬ^＊値が２５〜８５、ａ^＊値が−１００≦ａ^＊値＜０、ｂ^＊値が−１００≦ｂ^＊値≦＋１００及びｈ値が１２０°≦ｈ値≦２４０°であることが好ましい。
【００７７】
本発明に係る樹脂組成物中における緑色系顔料の配合割合は、樹脂１００重量部に対し０．５〜２００重量部の範囲で使用することができ、樹脂組成物のハンドリングを考慮すれば、好ましくは１．０〜１５０重量部、更に好ましくは２．５〜１００重量部である。
【００７８】
本発明に係る樹脂組成物における構成基材としては、緑色系顔料と周知の熱可塑性樹脂と共に、必要により、滑剤、可塑剤、酸化防止剤、紫外線吸収剤、各種安定剤等の添加剤が配合される。
【００７９】
樹脂としては、天然ゴム、合成ゴム、熱可塑性樹脂（例えば、ポリエチレン、ポリプロピレン、ポリブテン、ポリイソブチレン等のポリオレフィン、ポリ塩化ビニル、スチレン重合体、ポリアミド等）等を用いることができる。
【００８０】
添加剤の量は、緑色系顔料と樹脂との総和に対して５０重量％以下であればよい。添加剤の含有量が５０重量％を超える場合には、成形性が低下する。
【００８１】
本発明に係る樹脂組成物は、樹脂原料と緑色系顔料をあらかじめよく混合し、次に、混練機もしくは押出機を用いて加熱下で強いせん断作用を加えて、緑色系顔料の凝集体を破壊し、樹脂組成物中に緑色系顔料を均一に分散させた後、目的に応じた形状に成形加工して使用する。
【００８２】
次に本発明に係る緑色系顔料の製造法について述べる。
【００８３】
本発明に係る緑色系顔料は、含水酸化鉄粒子粉末とアルコキシシラン又はポリシロキサンを混合し、含水酸化鉄粒子粉末の粒子表面をアルコキシシラン又はポリシロキサンによって被覆し、次いで、アルコキシシラン又はポリシロキサンによって被覆された含水酸化鉄粒子粉末と有機青色顔料を混合することによって得ることができる。
【００８４】
含水酸化鉄粒子粉末の粒子表面へのアルコキシシラン又はポリシロキサンによる被覆は、含水酸化鉄粒子粉末とアルコキシシランの溶液又はポリシロキサンとを機械的に混合攪拌したり、含水酸化鉄粒子粉末にアルコキシシラン又はポリシロキサンを噴霧しながら機械的に混合攪拌すればよい。添加したアルコキシシラン又はポリシロキサンは、ほぼ全量が含水酸化鉄粒子粉末の粒子表面に被覆される。
【００８５】
なお、被覆されたアルコキシシランは、その一部が被覆工程を経ることによって生成する、アルコキシシランから生成するオルガノシラン化合物として被覆されていてもよい。この場合においてもその後の有機青色顔料の付着に影響することはない。
【００８６】
アルコキシシラン又はポリシロキサンを均一に含水酸化鉄粒子粉末の粒子表面に被覆するためには、含水酸化鉄粒子粉末の凝集をあらかじめ粉砕機を用いて解きほぐしておくことが好ましい。
【００８７】
芯粒子粉末とアルコキシシラン又はポリシロキサンとの混合攪拌や前記有機青色顔料と粒子表面にアルコキシシランから生成するオルガノシラン化合物又はポリシロキサンが被覆されている芯粒子粉末との混合攪拌をするための機器としては、粉体層にせん断力を加えることのできる装置が好ましく、殊に、せん断、へらなで及び圧縮が同時に行える装置、例えば、ホイール型混練機、ボール型混練機、ブレード型混練機、ロール型混練機を用いることができる。本発明の実施にあたっては、ホイール型混練機がより効果的に使用できる。
【００８８】
上記ホイール型混練機としては、具体的に、エッジランナー（「ミックスマラー」、「シンプソンミル」、「サンドミル」と同義語である）、マルチマル、ストッツミル、ウエットパンミル、コナーミル、リングマラー等があり、好ましくはエッジランナー、マルチマル、ストッツミル、ウエットパンミル、リングマラーであり、より好ましくはエッジランナーである。上記ボール型混練機としては、具体的に、振動ミル等がある。上記ブレード型混練機としては、具体的に、ヘンシェルミキサー、プラネタリーミキサー、ナウタミキサー等がある。上記ロール型混練機としては、具体的に、エクストルーダー等がある。
【００８９】
混合撹拌時における条件は、含水酸化鉄粒子粉末の粒子表面にアルコキシシラン又はポリシロキサンができるだけ均一に被覆されるように、線荷重は１９．６〜１９６０Ｎ／ｃｍ（２〜２００Ｋｇ／ｃｍ）、好ましくは９８〜１４７０Ｎ／ｃｍ（１０〜１５０Ｋｇ／ｃｍ）、より好ましくは１４７〜９８０Ｎ／ｃｍ（１５〜１００Ｋｇ／ｃｍ）、処理時間は５〜１２０分、好ましくは１０〜９０分の範囲で処理条件を適宜調整すればよい。なお、撹拌速度は２〜２０００ｒｐｍ、好ましくは５〜１０００ｒｐｍ、より好ましくは１０〜８００ｒｐｍの範囲で処理条件を適宜調整すればよい。
【００９０】
アルコキシシラン又はポリシロキサンの添加量は、含水酸化鉄粒子粉末１００重量部に対して０．１５〜４５重量部が好ましい。０．１５重量部未満の場合には、目的とする緑色系顔料を得られるだけの有機青色顔料を付着させることが困難である。０．１５〜４５重量部の添加量により、含水酸化鉄粒子粉末１００重量部に対して、有機青色顔料を５〜３０重量部付着させることができるので、４５重量部を超えて必要以上に添加する意味がない。
【００９１】
次いで、アルコキシシラン又はポリシロキサンを被覆した含水酸化鉄粒子粉末に、有機青色顔料を添加し、混合攪拌して、アルコキシシラン被覆又はポリシロキサン被覆に有機青色顔料を付着させる。必要により更に、乾燥乃至加熱処理を行ってもよい。
【００９２】
有機青色顔料は、少量ずつを時間をかけながら、殊に５〜６０分間程度をかけて添加するのが好ましい。
【００９３】
混合攪拌時における条件は、有機青色顔料が均一に付着するように、線荷重は１９．６〜１９６０Ｎ／ｃｍ（２〜２００Ｋｇ／ｃｍ）、好ましくは９８〜１４７０Ｎ／ｃｍ（１０〜１５０Ｋｇ／ｃｍ）、より好ましくは１４７〜９８０Ｎ／ｃｍ（１５〜１００Ｋｇ／ｃｍ）、処理時間は５〜１２０分、好ましくは１０〜９０分の範囲で処理条件を適宜調整すればよい。なお、撹拌速度は２〜２０００ｒｐｍ、好ましくは５〜１０００ｒｐｍ、より好ましくは１０〜８００ｒｐｍの範囲で処理条件を適宜調整すればよい。
【００９４】
有機青色顔料の添加量は、含水酸化鉄粒子粉末１００重量部に対して５〜３０重量部である。有機青色顔料の添加量が上記範囲外の場合には、目的とする緑色系顔料が得られない。
【００９５】
乾燥乃至加熱工程における加熱温度は、通常４０〜２００℃が好ましく、より好ましくは６０〜１５０℃である。処理時間は１０分〜１２時間が好ましく、３０分〜３時間がより好ましい。
【００９６】
含水酸化鉄粒子粉末は、必要により、アルコキシシラン又はポリシロキサンとの混合撹拌に先立って、あらかじめ、アルミニウムの水酸化物、アルミニウムの酸化物、ケイ素の水酸化物及びケイ素の酸化物より選ばれる少なくとも一種からなる中間被覆物で被覆しておいてもよい。
【００９７】
中間被覆物による被覆は、含水酸化鉄粒子粉末を分散して得られる水懸濁液に、アルミニウム化合物、ケイ素化合物又は当該両化合物を添加して混合攪拌することにより、又は、必要により、混合攪拌後にｐＨ値を調整することにより、前記含水酸化鉄粒子粉末の粒子表面を、アルミニウムの水酸化物、アルミニウムの酸化物、ケイ素の水酸化物及びケイ素の酸化物より選ばれる少なくとも一種からなる中間被覆物で被覆し、次いで、濾別、水洗、乾燥、粉砕する。必要により、更に、脱気・圧密処理等を施してもよい。
【００９８】
アルミニウム化合物としては、酢酸アルミニウム、硫酸アルミニウム、塩化アルミニウム、硝酸アルミニウム等のアルミニウム塩や、アルミン酸ナトリウム等のアルミン酸アルカリ塩等が使用できる。
【００９９】
ケイ素化合物としては、３号水ガラス、オルトケイ酸ナトリウム、メタケイ酸ナトリウム等が使用できる。
【０１００】
【発明の実施の形態】
本発明の代表的な実施の形態は、次の通りである。
【０１０１】
粒子の平均長軸径、平均短軸径は、いずれも電子顕微鏡写真を縦方向及び横方向にそれぞれ４倍に拡大した写真に示される粒子３５０個の長軸径、短軸径をそれぞれ測定し、その平均値で示した。
【０１０２】
軸比は、平均長軸径と平均短軸径との比で示した。
【０１０３】
粒子の長軸径の粒度分布は、下記の方法により求めた値で示した。
【０１０４】
即ち、上記拡大写真に示される粒子の長軸径を測定した値を、その測定値から計算して求めた粒子の実際の長軸径と個数から統計学的手法に従って対数正規確率紙上に横軸に長軸径を、縦軸に所定の長軸径区間のそれぞれに属する粒子の累積個数（積算フルイ下）を百分率でプロットする。そして、このグラフから粒子の個数が５０％及び８４．１３％のそれぞれに相当する長軸径の値を読みとり、幾何標準偏差値＝積算フルイ下８４．１３％における長軸径／積算フルイ下５０％における長軸径（幾何平均径）に従って算出した値で示した。幾何標準偏差値が１に近いほど、粒子の粒度分布が優れていることを意味する。
【０１０５】
比表面積値は、ＢＥＴ法により測定した値で示した。
【０１０６】
含水酸化鉄粒子粉末及び緑色系顔料の粒子内部や粒子表面に存在しているＡｌ量、Ｓｉ量及びアルコキシシランから生成するオルガノシラン化合物又はポリシロキサンに含有されているＳｉ量のそれぞれは、「蛍光Ｘ線分析装置３０６３Ｍ型」（理学電機工業株式会社製）を使用し、ＪＩＳ Ｋ０１１９の「けい光Ｘ線分析通則」に従って測定した。
【０１０７】
尚、含水酸化鉄粒子粉末の粒子表面を被覆しているケイ素の酸化物、ケイ素の水酸化物及びアルコキシシランから生成するオルガノシラン化合物に含有されるＳｉ又はポリシロキサンに含有されるＳｉの各Ｓｉ量は、処理工程後の各段階でＳｉ量を測定し、その測定値から処理工程前の段階で測定したＳｉ量を差し引いた値で示した。
【０１０８】
緑色系顔料に付着している有機青色顔料の被覆量は、「堀場金属炭素・硫黄分析装置ＥＭＩＡ−２２００型」（株式会社堀場製作所製）を用いて炭素量を測定することにより求めた。
【０１０９】
緑色系顔料に付着している有機青色顔料の脱離率（％）は、下記の方法により求めた値で示した。有機青色顔料の脱離率が０％に近いほど、緑色系顔料の粒子表面からの有機青色顔料の脱離量が少ないことを示す。
【０１１０】
緑色系顔料３ｇとエタノール４０ｍｌを５０ｍｌの沈降管に入れ、２０分間超音波分散を行った後、１２０分静置し、沈降速度によって緑色系顔料と脱離した有機青色顔料とを分離した。次いで、この緑色系顔料に再度エタノール４０ｍｌを加え、更に２０分間超音波分散を行った後１２０分静置し、緑色系顔料と脱離した有機青色顔料を分離した。この緑色系顔料を８０℃で１時間乾燥させ、有機青色顔料の量を測定し、下記数１に従って求めた値を有機青色顔料の脱離率（％）とした。
【０１１１】
【数１】
有機青色顔料の脱離率（％）＝{（Ｗａ−Ｗｅ）／Ｗａ}×１００
Ｗａ：緑色系顔料の有機青色顔料付着量
Ｗｅ：脱離テスト後の緑色系顔料の有機青色顔料付着量
【０１１２】
含水酸化鉄粒子粉末及び緑色系顔料の色相は、試料０．５ｇとヒマシ油０．５ｍｌとをフーバー式マーラーで練ってペースト状とし、このペーストにクリアラッカー４．５ｇを加え、混練、塗料化してキャストコート紙上に１５０μｍ（６ｍｉｌ）のアプリケーターを用いて塗布した塗布片（塗膜厚み：約３０μｍ）を作製し、 該塗布片について、多光源分光測色計（ＭＳＣ−ＩＳ−２Ｄ、スガ試験機株式会社製）Ｍｕｌｔｉ−ｓｐｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いてＬ^＊値、ａ^＊値及びｂ^＊値を測定した。
【０１１３】
なお、ｈ値は上記測定で得られたａ^＊値及びｂ^＊値を用い、下記数２に従って求めることができる。
【０１１４】
【数２】
ｈ＝ｔａｎ^−１（ｂ^＊／ａ^＊） （ａ^＊＞０，ｂ^＊≦０ の場合）
ｈ＝１８０＋ｔａｎ^−１（ｂ^＊／ａ^＊） （ａ^＊＜０の場合）
ｈ＝３６０＋ｔａｎ^−１（ｂ^＊／ａ^＊） （ａ^＊＞０，ｂ^＊＜０ の場合）
【０１１５】
緑色系顔料の耐熱性は、熱分析装置ＳＳＣ５０００（セイコー電子工業株式会社製）を用いて被測定粒子粉末の示差走査熱量測定（ＤＳＣ）を行い、得られた該ＤＳＣチャート上に示されるピークを形成する２つの変曲点のうち、最初の変曲点を構成する２つの曲線のそれぞれについて接線を引き、両接線の交点に対応する温度を読み取って、その温度で示した。
【０１１６】
含水酸化鉄粒子粉末、有機青色顔料及び緑色系顔料の着色力は、下記に示す方法に従って作製した原色エナメルと展色エナメルのそれぞれを、キャストコート紙上に１５０μｍ（６ｍｉｌ）のアプリケーターを用いて塗布して塗布片を作製し、 該塗布片について、多光源分光測色計（ＭＳＣ−ＩＳ−２Ｄ、スガ試験機株式会社製）Ｍｕｌｔｉ−ｓｐｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いてＬ^＊値を測色し、その差をΔＬ^＊値で示し、標準試料として用いたクロムグリーン（比較例６）のΔＬｓ^＊値とを用いて下記数３に従って算出した値を着色力（％）として示した。
【０１１７】
【数３】
着色力（％）＝１００＋{（ΔＬｓ^＊−ΔＬ^＊）×１０}
【０１１８】
原色エナメルの作製：
上記試料粉体１０ｇとアミノアルキッド樹脂１６ｇ及びシンナー６ｇとを配合して３ｍｍφガラスビーズ９０ｇと共に１４０ｍｌのガラスビンに添加し、次いで、ペイントシェーカーで４５分間混合分散した後、アミノアルキッド樹脂５０ｇを追加し、更に５分間ペイントシェーカーで分散させて、原色エナメルを作製した。
【０１１９】
展色エナメルの作製：
上記原色エナメル１２ｇとアミラックホワイト（二酸化チタン分散アミノアルキッド樹脂）４０ｇとを配合し、ペイントシェーカーで１５分間混合分散して、展色エナメルを作製した。
【０１２０】
含水酸化鉄粒子粉末、有機青色顔料及び緑色系顔料の隠蔽力は、上記で得られた原色エナメルを用いて、ＪＩＳ Ｋ ５１０１ ８．２のクリプトメーター法に従って得られた値で示した。
【０１２１】
含水酸化鉄粒子粉末、有機青色顔料及び緑色系顔料の耐酸性は、試料粉体１０ｇを５％の硫酸に１０分間浸漬し、次いで、試料を硫酸水溶液中から取り出して水洗した後乾燥させ、前述と同様の方法で塗布膜を作製し、Ｌ^＊値、ａ^＊値及びｂ^＊値を測色し、下記数４に従って算出した色差ΔＥ^＊値によって示した。ΔＥ^＊値が小さいほど、耐酸性に優れていることを示す。
【０１２２】
含水酸化鉄粒子粉末、有機青色顔料及び緑色系顔料の耐アルカリ性は、試料粉体１０ｇを１％の苛性ソーダ水溶液に１５分間浸漬し、次いで、試料を苛性ソーダ水溶液中から取り出して水洗した後乾燥させ、前述と同様の方法で塗布膜を作製し、Ｌ^＊値、ａ^＊値及びｂ^＊値を測色し、下記数４に従って算出した色差ΔＥ^＊値によって示した。ΔＥ^＊値が小さいほど、耐アルカリ性に優れていることを示す。
【０１２３】
【数４】
ΔＥ^＊値＝（（ΔＬ^＊）^２＋（Δａ^＊）^２＋（Δｂ^＊）^２）^１／２
ΔＬ^＊値：試料粉体の酸又はアルカリ浸漬処理前後のＬ^＊値の差
Δａ^＊値：試料粉体の酸又はアルカリ浸漬処理前後のａ^＊値の差
Δｂ^＊値：試料粉体の酸又はアルカリ浸漬処理前後のｂ^＊値の差
【０１２４】
緑色系顔料を用いて得られた溶剤系塗料及び水系塗料の各塗膜の色相は、後述する処方によって調製した各塗料を冷間圧延鋼板（０．８ｍｍ×７０ｍｍ×１５０ｍｍ）（ＪＩＳ Ｇ−３１４１）に１５０μｍの厚みで塗布、乾燥して塗膜を形成することによって得られた測定用塗布片を用い、緑色系顔料を用いて着色した樹脂組成物の色相は、後述する処法によって作製した着色樹脂プレートを用いて、該塗布片及び該プレートを、それぞれ、多光源分光測色計（ＭＳＣ−ＩＳ−２Ｄ、スガ試験機株式会社製）Ｍｕｌｔｉ−ｓｐｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いてＬ^＊値、ａ^＊値及びｂ^＊値の測定を行った。
【０１２５】
尚、ｈ値は上記測定で得られたａ^＊値及びｂ^＊値の測定を用い、上記数２に従って求めた。
【０１２６】
塗膜の光沢度は、上記測定用塗布片を「グロスメーター ＵＧＶ−５Ｄ」（スガ試験機株式会社製）を用いて入射角６０°の時の光沢度で示した。光沢度が高いほど、緑色系顔料を配合した塗料の分散性が優れていることを示す。
【０１２７】
緑色系顔料を用いた塗膜の耐熱性は、上記測定用塗布片を電気炉に入れ、電気炉の温度を種々変化させて各温度において１５分間加熱処理を行い、塗布片の各温度における加熱前後での色相（Ｌ^＊値、ａ^＊値、ｂ^＊値）を、多光源分光測色計（ＭＳＣ−ＩＳ−２Ｄ、スガ試験機株式会社製）Ｍｕｌｔｉ−ｓｐｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いて測定し、加熱前の測色値を基準に下記数５で示されるΔＥ^＊値を求め、片対数グラフを用いて横軸に加熱温度を、縦軸にΔＥ^＊値をプロットし、ΔＥ^＊値がちょうど１．５となるときの温度を塗膜の耐熱温度とした。
【０１２８】
【数５】
ΔＥ^＊値＝（（ΔＬ^＊値）^２＋（Δａ^＊値）^２＋（Δｂ^＊値）^２）^１／２
ΔＬ^＊値： 比較する塗膜の加熱処理前後のＬ^＊値の差
Δａ^＊値： 比較する塗膜の加熱処理前後のａ^＊値の差
Δｂ^＊値： 比較する塗膜の加熱処理前後のｂ^＊値の差
【０１２９】
緑色系顔料を用いて得られた塗料の貯蔵安定性は、後出の所定の組成分を所定割合で配合し、ミルベースを９０分間分散させて得られた塗料を冷間圧延鋼板（０．８ｍｍ×７０ｍｍ×１５０ｍｍ）（ＪＩＳ−Ｇ−３１４１）に１５０μｍの厚みで塗布、乾燥して製造した塗膜の色相Ｌ^＊値、ａ^＊値及びｂ^＊値と、該塗料を２５℃において１週間静置して得られた塗料を冷間圧延鋼板に塗布、乾燥して製造した塗膜の色相を測定し、下記数６に従って得られたΔＥ^＊値で示した。
【０１３０】
【数６】
ΔＥ^＊値＝（（ΔＬ^＊）^２＋（Δａ^＊）^２＋（Δｂ^＊）^２）^１／２
ΔＬ^＊値： 比較する塗膜の静置前後のＬ^＊値の差
Δａ^＊値： 比較する塗膜の静置前後のａ^＊値の差
Δｂ^＊値： 比較する塗膜の静置前後のｂ^＊値の差
【０１３１】
塗膜の耐酸性は、後出の所定の組成分を所定割合で配合して得られた塗料を、冷間圧延鋼板（０．８ｍｍ×７０ｍｍ×１５０ｍｍ：ＪＩＳ Ｇ−３１４１）に１５０μｍの厚みで塗布、乾燥して製造した塗膜を有する試料を用意し、光沢度を測定しておく。次に、１０００ｍｌのビーカーに５重量％硫酸水溶液を入れ、上記塗布片を糸でつるして約１２０ｍｍの深さまで浸し、２５℃で２４時間静置する。
【０１３２】
次に、塗布片を硫酸水溶液中から取り出して流水で静かに洗い、水を振り切った後、塗布片の中心部分の光沢度を測定する。そして硫酸水溶液への浸漬前後の光沢度変化（ΔＧ値）を測定し、これの大小で耐酸性を評価した。ΔＧ値が小さいほど、耐酸性に優れていることを示す。
【０１３３】
塗膜の耐アルカリ性は、後出の所定の組成分を所定割合で配合して得られた塗料を、冷間圧延鋼板（０．８ｍｍ×７０ｍｍ×１５０ｍｍ：ＪＩＳ Ｇ−３１４１）に１５０μｍの厚みで塗布、乾燥して製造した塗膜を有する試料を用意し、光沢度を測定しておく。次に、１０００ｍｌのビーカーに１％苛性ソーダ水溶液を入れ、上記塗布片を糸でつるして約１２０ｍｍの深さまで浸し、２５℃で２４時間静置する。
【０１３４】
次に、塗布片を苛性ソーダ水溶液中から取り出して流水で静かに洗い、水を振り切った後、塗布片の中心部分の光沢度を測定する。そして硫酸水溶液への浸漬前後の光沢度変化（ΔＧ値）を測定し、これの大小で耐アルカリ性を評価した。
ΔＧ値が小さいほど、耐アルカリ性に優れていることを示す。
【０１３５】
緑色系顔料を用いて着色した樹脂組成物の耐熱性は、後述する処方によって作製した着色樹脂プレートを５ｃｍ角に裁断し、該着色樹脂プレートをホットプレスにかけ、ホットプレス温度を種々変化させて、各温度において９８ＭＰａ（１トン／ｃｍ^２）の荷重をかけながら１０分間加熱処理を行い、着色樹脂プレートの各温度における加熱前後での色相（Ｌ^＊値、ａ^＊値、ｂ^＊値）を多光源分光測色計（ＭＳＣ−ＩＳ−２Ｄ、スガ試験機株式会社製）Ｍｕｌｔｉ−ｓｐｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いて測定し、加熱前の測色値を基準に下記数７で示されるΔＥ^＊値を求め、片対数グラフを用いて横軸に加熱温度を、縦軸にΔＥ^＊値をプロットし、ΔＥ^＊値がちょうど１．５となるときの温度を樹脂組成物の耐熱温度とした。
【０１３６】
【数７】
ΔＥ^＊値＝（（ΔＬ^＊値）^２＋（Δａ^＊値）^２＋（Δｂ^＊値）^２）^１／２
ΔＬ^＊値：比較する着色樹脂プレートの加熱処理前後のＬ^＊値の差
Δａ^＊値：比較する着色樹脂プレートの加熱処理前後のａ^＊値の差
Δｂ^＊値：比較する着色樹脂プレートの加熱処理前後のｂ^＊値の差
【０１３７】
塗料粘度については、後述する処方によって調製した塗料の２５℃のおける塗料粘度をＥ型粘度計（コーンプレート型粘度計）ＥＭＤ−Ｒ（株式会社東京計器製）を用いて、ずり速度Ｄ＝１．９２ ｓｅｃ^−１における値を求めた。
【０１３８】
緑色系顔料の樹脂組成物への分散性は、得られた着色樹脂プレート表面における未分散の凝集粒子の個数を目視により判定し、５段階で評価した。５が最も分散状態が良いことを示す。
５： 未分散物認められず、
４： １ｃｍ^２当たり１個以上５個未満、
３： １ｃｍ^２当たり５個以上１０個未満、
２： １ｃｍ^２当たり１０個以上５０個未満、
１： １ｃｍ^２当たり５０個以上。
【０１３９】
＜緑色系顔料の製造＞
ゲータイト粒子粉末（粒子形状：針状、平均長軸径０．４０μｍ、軸比５．３、幾何標準偏差値１．４４、ＢＥＴ比表面積値１８．８ｍ^２／ｇ、Ｌ^＊値５９．３、ａ^＊値１６．５、ｂ^＊値５３．９、ｈ値７３．０°、耐熱性１９８℃）１１．０ｋｇをエッジランナー「ＭＰＵＶ−２型」（製品名、株式会社松本鋳造鉄工所製）に投入し、メチルトリエトキシシラン（商品名：ＴＳＬ８１２３：東芝シリコーン株式会社製）２２０ｇを２００ｍｌのエタノールで混合希釈して得られるメチルトリエトキシシラン溶液を、エッジランナーを稼動させながら上記ゲータイト粒子粉末に添加し、３９２Ｎ／ｃｍ（４０Ｋｇ／ｃｍ）の線荷重で２０分間混合攪拌を行った。なお、このときの撹拌速度は２２ｒｐｍで行った。
【０１４０】
次に、有機青色顔料Ａ（種類：フタロシアニンブルー、粒子形状：粒状、平均長軸径０．０６μｍ、隠蔽力２４０ｃｍ^２／ｇ、Ｌ^＊値１７．７、ａ^＊値９．７、ｂ^＊値−２３．４、ｈ値２９２．５°、耐熱性２５６℃）８２５ｇを、エッジランナーを稼動させながら１０分間かけて添加し、更に３９２Ｎ／ｃｍ（４０Ｋｇ／ｃｍ）の線荷重で２０分間、混合攪拌を行い、メチルトリエトキシシラン被覆の上に有機青色顔料Ａを付着させた後、乾燥器を用いて１０５℃で６０分間加熱処理を行い、緑色系顔料を得た。なお、このときの撹拌速度は２２ｒｐｍで行った。
【０１４１】
得られた緑色系顔料は、平均長軸径が０．４０μｍ、軸比が５．３の針状粒子粉末であった。幾何標準偏差値は１．４４、ＢＥＴ比表面積値は２０．１ｍ^２／ｇ、Ｌ^＊値は３９．９、ａ^＊値は−１３．２、ｂ^＊値は＋１９．８、ｈ値は１２３．７°、着色力は１４１％、隠蔽力は１，９５０ｃｍ^２／ｇであり、耐薬品性のうち、耐酸性はΔＥ^＊値で０．９９、耐アルカリ性はΔＥ^＊値で０．８６であり、耐熱性は２２７℃、有機青色顔料の脱離率は７．０％であり、メチルトリエトキシシランから生成したオルガノシラン化合物の被覆量はＳｉ換算で０．２９重量％、付着している有機青色顔料の量は、Ｃ換算で４．６１重量％（ゲータイト粒子粉末１００重量部に対して７．５重量部に相当する）であった。
【０１４２】
電子顕微鏡写真観察の結果、有機青色顔料がほとんど認められないことから、有機青色顔料のほぼ全量がメチルトリエトキシシランから生成するオルガノシラン化合物被覆に付着していることが認められた。
【０１４３】
＜緑色系顔料を含む溶剤系塗料の製造＞
上記緑色系顔料１０ｇとアミノアルキッド樹脂及びシンナーとを下記割合で配合して３ｍｍφガラスビーズ９０ｇと共に１４０ｍｌのガラスビンに添加し、次いで、ペイントシェーカーで９０分間混合分散し、ミルベースを作製した。
【０１４４】
緑色系顔料 １２．２重量部、
アミノアルキッド樹脂 １９．５重量部、
（アミラックＮｏ．１０２６：関西ペイント株式会社製）
シンナー ７．３重量部。
【０１４５】
上記ミルベースを用いて、下記割合となるようにアミノアルキッド樹脂を配合し、ペイントシェーカーで更に１５分間混合分散して、緑色系顔料を含む溶剤系塗料を得た。
【０１４６】
ミルベース ３９．０重量部、
アミノアルキッド樹脂 ６１．０重量部。
（アミラックＮｏ．１０２６：関西ペイント株式会社製）
【０１４７】
得られた溶剤系塗料の塗料粘度は１，４５２ｃＰ、塗料の貯蔵安定性は、ΔＥ^＊値で０．９２であった。
【０１４８】
次いで、上記溶剤系塗料を冷間圧延鋼板（０．８ｍｍ×７０ｍｍ×１５０ｍｍ）（ＪＩＳ Ｇ−３１４１）に１５０μｍの厚みで塗布、乾燥して得られた塗膜の光沢度は８７％、塗膜の耐熱温度は２４９℃であり、色相はＬ^＊値が４０．２、ａ^＊値が−１２．４、ｂ^＊値が＋２０．５、ｈ値が１２１．２°、耐酸性はΔＧ値で９．３％、耐アルカリ性はΔＧ値で７．９％であった。
【０１４９】
＜緑色系顔料を含む水系塗料の製造＞
上記緑色系顔料７．６２ｇと水溶性アルキッド樹脂等とを下記割合で３ｍｍφガラスビーズ９０ｇと共に１４０ｍｌのガラスビンに添加し、次いでペイントシェーカーで９０分間混合分散し、ミルベースを作製した。
【０１５０】
緑色系顔料 １２．４重量部、
水溶性アルキッド樹脂 ９．０重量部、
（商品名：Ｓ−１１８：大日本インキ化学工業株式会社製）
消泡剤 ０．１重量部、
（商品名：ノプコ８０３４：サンノプコ株式会社製）
水 ４．８重量部、
ブチルセロソルブ ４．１重量部。
【０１５１】
上記ミルベースを用いて、塗料組成を下記割合で配合してペイントシェーカーで更に１５分間混合分散し水溶性塗料を得た。
【０１５２】
ミルベース ３０．４重量部、
水溶性アルキッド樹脂 ４６．２重量部、
（商品名：Ｓ−１１８：大日本インキ化学工業株式会社製）
水溶性メラミン樹脂 １２．６重量部、
（商品名：Ｓ−６９５：大日本インキ化学工業株式会社製）
消泡剤 ０．１重量部、
（商品名：ノプコ８０３４：サンノプコ株式会社製）
水 ９．１重量部、
ブチルセロソルブ １．６重量部。
【０１５３】
得られた水系塗料の塗料粘度は２，１１８ｃＰ、貯蔵安定性はΔＥ^＊値で１．００であった。
【０１５４】
次いで、上記水系塗料を冷間圧延鋼板（０．８ｍｍ×７０ｍｍ×１５０ｍｍ）（ＪＩＳ Ｇ−３１４１）に１５０μｍの厚みで塗布、乾燥して得られた塗膜の光沢度は８２％、塗膜の耐熱温度は２４７℃であり、色相はＬ^＊値が４０．７、ａ^＊値が−１２．６、ｂ^＊値が＋２０．９、ｈ値が１２１．１°、耐酸性はΔＧ値で９．６％、耐アルカリ性はΔＧ値で８．８％であった。
【０１５５】
＜樹脂組成物の製造＞
上記緑色系顔料２．５ｇとポリ塩化ビニル樹脂粉末１０３ＥＰ８Ｄ（日本ゼオン株式会社製）４７．５ｇとを秤量し、これらを１００ｍｌポリビーカーに入れ、スパチュラでよく混合して混合粉末を得た。
【０１５６】
得られた混合粉末にステアリン酸カルシウムを０．５ｇ加えて混合し、１６０℃に加熱した熱間ロールのクリアランスを０．２ｍｍに設定した後、上記混合粉末を少しずつロールにて練り込んで樹脂組成物が一体となるまで混練を続けた後、樹脂組成物をロールから剥離して着色樹脂プレート原料として用いた。
【０１５７】
次に、表面研磨されたステンレス板の間に上記樹脂組成物を挟んで１８０℃に加熱したホットプレス内に入れ、１トン／ｃｍ^２の圧力で加圧成形して厚さ１ｍｍの着色樹脂プレートを得た。得られた着色樹脂プレートの分散状態は５であり、着色樹脂プレートの耐熱温度は２２３℃、色相は、Ｌ^＊値が４２．２、ａ^＊値が−１０．８、ｂ^＊値が＋１７．９、ｈ値が１２１．１°であった。
【０１５８】
【作用】
本発明において最も重要な点は、含水酸化鉄粒子粉末の粒子表面がアルコキシシランから生成するオルガノシラン化合物又はポリシロキサンによって被覆されていると共に、該被覆に有機青色顔料が付着している緑色系顔料は、耐薬品性に優れ、且つ、隠蔽力及び着色力が大きく、しかも耐熱性が向上した無害な緑色系顔料であるという事実である。
【０１５９】
本発明において緑色を呈する顔料が得られる理由としては、黄色のフィルムに青い透明フィルムを重ねると緑色を呈するのと同じ原理で、隠蔽力が弱い有機青色顔料によって黄色を呈する含水酸化鉄粒子粉末を被覆することによって、緑色に見えるものと考えている。
【０１６０】
本発明に係る緑色系顔料が耐薬品性に優れている理由としては、芯粒子粉末である含水酸化鉄粒子粉末が耐薬品性に優れていると共に、粒子粉末に付着させた有機青色顔料もまた耐薬品性に優れたものを選ぶことによって、粒子全体の耐薬品性がより向上したものと考えている。
【０１６１】
本発明に係る緑色系顔料が隠蔽力及び着色力に優れている理由としては、隠蔽力及び着色力に優れる含水酸化鉄粒子粉末の粒子表面にオルガノシラン化合物又はポリシロキサン被覆を介して有機青色顔料を強固に固定化して複合化できたことによって、隠蔽力と着色力が共に優れた顔料とすることができるものと考えている。
【０１６２】
本発明に係る緑色系顔料の耐熱性が優れている理由としては、本来耐熱性に劣る含水酸化鉄粒子粉末を耐熱性に優れたオルガノシラン化合物又はポリシロキサンによって被覆し、更に、耐熱性に優れている有機青色顔料が固定化されることによって、緑色系顔料としての耐熱性が向上したものと考えている。
【０１６３】
また、本発明に係る緑色系顔料は、有害な元素及び化合物を含有していないので、衛生面や安全性に優れ、また、環境汚染防止に配慮した顔料である。
【０１６４】
【実施例】
次に、実施例及び比較例を示す。
【０１６５】
芯粒子１〜４：
芯粒子粉末として表１に示す特性を有する含水酸化鉄粒子粉末を用意した。
【０１６６】
【表１】

【０１６７】
芯粒子５：
芯粒子１の針状ゲータイト粒子粉末２０ｋｇと水１５０ｌとを用いて、針状ゲータイト粒子粉末を含むスラリーを得た。得られた針状ゲータイト粒子粉末を含む再分散スラリーのｐＨ値を、水酸化ナトリウム水溶液を用いて１０．５に調整した後、該スラリーに水を加えスラリー濃度を９８ｇ／ｌに調整した。このスラリー１５０ｌを加熱して６０℃とし、このスラリー中に１．０ｍｏｌ／ｌのアルミン酸ナトリウム溶液２７２２ｍｌ（針状ゲータイト粒子粉末に対してＡｌ換算で０．５重量％に相当する）を加え、３０分間保持した後、酢酸を用いてｐＨ値を７．５に調整した。この状態で３０分間保持した後、濾過、水洗、乾燥、粉砕して粒子表面がアルミニウムの水酸化物により被覆されている針状ゲータイト粒子粉末を得た。
【０１６８】
このときの製造条件を表２に、得られた表面処理済みゲータイト粒子粉末の諸特性を表３に示す。
【０１６９】
芯粒子６〜８：
芯粒子２〜４の各含水酸化鉄粒子粉末を用い、表面被覆物の種類及び量を種々変化させた以外は、前記芯粒子５と同様にして粒子表面が被覆物で被覆されている含水酸化鉄粒子粉末を得た。
【０１７０】
このときの製造条件を表２に、得られた表面処理済み含水酸化鉄粒子粉末の諸特性を表３に示す。
【０１７１】
【表２】

【０１７２】
【表３】

【０１７３】
尚、表面処理工程における被覆物の種類のＡはアルミニウムの水酸化物であり、Ｓはケイ素の酸化物を表わす。
【０１７４】
有機青色顔料Ａ、Ｂ：
有機青色顔料として表４に示す諸特性を有するフタロシアニンブルーを用意した。
【０１７５】
【表４】

【０１７６】
実施例１〜８、比較例１〜５：
アルコキシシラン、ポリシロキサン、シリコン化合物による被覆工程における添加物の種類、添加量、エッジランナー処理の線荷重及び時間、有機青色顔料の付着工程における有機青色顔料の種類、添加量、エッジランナー処理の線荷重及び時間を種々変化させた以外は、前記発明の実施の形態と同様にして緑色系顔料を得た。
【０１７７】
このときの製造条件を表５に、得られた緑色系顔料の諸特性を表６に示す。
【０１７８】
比較例６〜８
比較例６としてクロムグリーン、比較例７として酸化クロム、比較例８としてフタロシアニングリーンのそれぞれ単独での諸特性を表６に示す。
【０１７９】
【表５】

【０１８０】
【表６】

【０１８１】
実施例９〜１６、比較例９〜１６：
緑色系顔料の種類を種々変化させた以外は、前記発明の実施の形態と同様にして塗料を得た。
【０１８２】
得られた塗料の諸特性及び塗膜の諸特性を表７に示す。
【０１８３】
【表７】

【０１８４】
実施例１７〜２４、比較例１７〜２４：
緑色系顔料の種類を種々変化させた以外は、前記発明の実施の形態と同様にして水系塗料を得た。
【０１８５】
得られた水系塗料の諸特性及び塗膜の諸特性を表８に示す。
【０１８６】
【表８】

【０１８７】
実施例２５〜３２、比較例２５〜３２：
緑色系顔料の種類を種々変化させた以外は、前記発明の実施の形態と同様にして樹脂組成物を得た。
【０１８８】
このときの製造条件及び得られた樹脂組成物の諸特性を表９に示す。
【０１８９】
【表９】

【０１９０】
【発明の効果】
本発明に係る緑色系顔料は、隠蔽力及び着色力が大きく、耐熱性及び耐候性に優れ、しかも、無害であることから緑色系顔料として好適である。
【０１９１】
本発明に係る塗料及び樹脂組成物は、耐熱性及び耐薬品性に優れ、且つ、無害である緑色系顔料を用いることから環境汚染を配慮した緑色系塗料及び樹脂組成物として好適である。[0001]
[Industrial application fields]
The present invention provides a harmless green pigment having excellent chemical resistance such as acid resistance and alkali resistance, large hiding power and coloring power, and improved heat resistance.
[0002]
[Prior art]
Currently, chromium green, chromium oxide, zinc green, phthalocyanine green, and the like are used as green pigments, and are widely used as colored pigments for resins, paints, printing inks, and the like.
[0003]
Chrome green is excellent in light resistance, but inferior in chemical resistance such as acid and alkali, and chromium oxide is excellent in light resistance, heat resistance and chemical resistance, but has low hiding power and coloring power, It is known to be expensive.
[0004]
In addition, green inorganic pigments such as chromium green, chromium oxide and zinc green are toxic because they contain lead and chromium as their constituent elements, so from the viewpoints of hygiene, safety and environmental pollution prevention There is a strong demand for alternative green pigments.
[0005]
On the other hand, organic green pigments such as phthalocyanine green are known to have a clear color tone but weak hiding power.
[0006]
Therefore, there is a strong demand for harmless green pigments that are excellent in chemical resistance and have excellent hiding power and coloring power.
[0007]
Conventionally, techniques for combining inorganic pigments and organic pigments to improve various properties as pigments have been attempted. For example, coprecipitation of chrome lead and phthalocyanine blue or adhesion of organic pigments to the surface of inorganic pigment particles Methods (JP-A-4-132770, JP-A-10-88032, etc.) have been proposed.
[0008]
[Problems to be solved by the invention]
A harmless green pigment having excellent chemical resistance, large hiding power and coloring power, and improved heat resistance is currently most demanded, but has not yet been obtained.
[0009]
That is, in the method of coprecipitation of yellow lead and phthalocyanine blue described above, since the yellow lead is used, it is toxic and manufactured by coprecipitation. In such a case, it is difficult to say that the storage stability is sufficient, and in the case of a coating film, color floating may occur, which is not preferable.
[0010]
Further, the method described in the above-mentioned JP-A-4-132770 is a method for depositing an organic pigment in the presence of an inorganic pigment, and it is difficult to say that the adhesion strength of the organic pigment is sufficient. The method described in the above-mentioned JP-A-10-88032 is a method of mechanically mixing and grinding an inorganic pigment and an organic pigment, and it is difficult to say that the adhesion strength of the organic pigment is sufficient.
[0011]
In JP-A-11-323174, the surface of black iron oxide particles or black hydrated iron oxide particles is coated with an organosilane compound formed from alkoxysilane, and the organosilane compound coating is coated with carbon black. Although the iron-based black composite particle powder to which is attached is described, this is a technique for fixing black carbon black to black inorganic particles, which is different from the technique for obtaining a green pigment.
[0012]
Therefore, the present invention provides a green pigment that is harmless, has excellent chemical resistance such as acid resistance and alkali resistance, has high hiding power and coloring power, and has improved heat resistance. Let it be an issue.
[0013]
[Means for solving the problems]
The technical problem can be achieved by the present invention as follows.
[0014]
That is, according to the present invention, the average major axis diameter of 0.1% in which the particle surface of the hydrous iron oxide particle powder is coated with an organosilane compound or polysiloxane generated from alkoxysilane and the organic blue pigment is attached to the coating. It is composed of a composite hydrous iron oxide particle powder of ~ 1.0 μm,The coating amount of the organosilane compound or polysiloxane is 0.02 to 5.0% by weight in terms of Si with respect to the organosilane compound-coated hydrous iron oxide particle powder or the polysiloxane-coated hydrous iron oxide particle powder,The organic blue pigment is a green pigment characterized in that the adhesion amount of the organic blue pigment is 5 to 30 parts by weight with respect to 100 parts by weight of the hydrous iron oxide particle powder (Invention 1).
[0015]
Further, in the present invention, the particle surface of the hydrous iron oxide particle powder of the present invention 1 is an intermediate comprising at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide in advance. It is a green pigment characterized by being covered with a coating (Invention 2).
[0016]
Further, the present invention is a paint characterized in that the green pigment according to the present invention 1 or the present invention 2 is blended in a paint constituting base material.
[0017]
The present invention is also a resin composition characterized by being colored using the green pigment according to the first or second aspect of the present invention.
[0018]
The configuration of the present invention will be described in more detail as follows.
[0019]
First, the green pigment according to the present invention will be described.
[0020]
In the green pigment according to the present invention, the surface of the hydrous iron oxide particles as the core particles is coated with an organosilane compound or polysiloxane generated from alkoxysilane, and the organic blue pigment is attached to the coating. It consists of green composite iron oxide particles having an average major axis diameter of 0.1 to 1.0 μm.
[0021]
The shape of the hydrous iron oxide particles in the present invention is needle-shaped or rectangular parallelepiped. Here, the “needle shape” means not only a literal needle shape but also a spindle shape and a rice grain shape.
[0022]
The hydrous iron oxide particle powder in the present invention is a goethite (α-FeOOH) particle powder, a goethite particle powder containing 0.05 to 50% by weight of aluminum in terms of Al in the particle and a lipid docrosite (γ- FeOOH) particle powder, and considering the hue of the green pigment to be obtained, goethite particle powder and goethite particle powder containing 0.05 to 50% by weight of aluminum in terms of Al inside the particle are preferable.
[0023]
The average major axis diameter of the hydrous iron oxide powder is 0.1 to 1.0 μm, preferably 0.15 to 0.9 μm.
[0024]
When the average major axis diameter exceeds 1.0 μm, the obtained green pigment also becomes coarse particles, and the coloring power decreases. When the average major axis diameter is less than 0.1 μm, aggregation is likely to occur due to an increase in intermolecular force due to finer particles, so that the surface of the hydrous iron oxide powder particles is uniformly coated with alkoxysilane or polysiloxane. Processing and uniform adhesion treatment with organic blue pigments become difficult.
[0025]
The axial ratio (the ratio between the average major axis diameter and the average minor axis diameter) of the hydrous iron oxide particle powder in the present invention (hereinafter referred to as “axial ratio”) is preferably 20 or less, more preferably 2 to 15, and still more preferably. Is 2-10.
[0026]
When the axial ratio exceeds 20, the entanglement of the particles increases, and it becomes difficult to uniformly coat the surface of the hydrated iron oxide particle powder with alkoxysilane or polysiloxane and uniformly adhere with the organic blue pigment. .
[0027]
The geometric standard deviation value of the major axis diameter of the hydrous iron oxide powder is preferably 2.0 or less, more preferably 1.8 or less, and still more preferably 1.6 or less. When the geometric standard deviation value exceeds 2.0, uniform dispersion is hindered by the coarse particles present, so that the surface of the hydrous iron oxide particle powder is uniformly coated with alkoxysilane or polysiloxane and organic. A uniform adhesion treatment with a blue pigment becomes difficult. The lower limit value of the geometric standard deviation value is 1.01, and those less than 1.01 are difficult to obtain industrially.
[0028]
The BET specific surface area of the hydrous iron oxide powder is 5 to 150 m.²/ G is preferable, more preferably 10 to 120 m.²/ G, even more preferably 15-100 m²/ G. BET specific surface area value is 5m²When the amount is less than / g, the hydrous iron oxide particle powder is coarse or particles are sintered between the particles, and the resulting green composite hydrous iron oxide particles are also coarse particles, resulting in coloring power. Decreases. BET specific surface area value is 150m²/ G exceeding, it tends to cause agglomeration due to an increase in intermolecular force due to the refinement of the particles. Therefore, uniform coating treatment with alkoxysilane or polysiloxane on the surface of the hydrated iron oxide particle powder and organic blue pigment. A uniform adhesion process becomes difficult.
[0029]
The hue of the hydrous iron oxide particle powder in the present invention is L^*Value is 40-80, a^*The value is -57.7 ≦ a^*Value ≦ + 57.7 (a value ≠ 0), b^*The value is 0 <b^*The value ≦ + 100 and the h value are in the range of 0 <h value <120 °. L^*Value, a^*Value, b^*When the value and h value are outside the above ranges, it is difficult to obtain the green pigment targeted by the present invention.
[0030]
The hydrous iron oxide powder in the present invention preferably has a heat resistance of 180 ° C. or higher, more preferably 185 ° C. or higher. Considering the heat resistance of the obtained green composite hydrous iron oxide particle powder, it is preferable to use a goethite particle powder containing 0.05 to 50% by weight of aluminum in terms of Al as the core particle powder, In that case, the heat resistant temperature is about 250 ° C.
[0031]
The organosilane compound (hereinafter referred to as “organosilane compound”) produced from the alkoxysilane in the present invention is an organosilane compound produced from the alkoxysilane represented by Chemical Formula 1 through a drying or heating step.
[0032]
[Chemical 1]

[0033]
Specific examples of the alkoxysilane include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane. Examples include methoxysilane and decyltrimethoxysilane.
[0034]
In view of the adhesion effect and desorption rate of the organic blue pigment, an organosilane compound formed from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, and phenyltriethoxysilane is preferred, and methyltriethoxysilane An organosilane compound produced from methyltrimethoxysilane is more preferred.
[0035]
As the polysiloxane in the present invention, a polysiloxane represented by Chemical Formula 2, a modified polysiloxane represented by Chemical Formula 3, a terminal modified polysiloxane represented by Chemical Formula 4, or a mixture thereof can be used.
[0036]
[Chemical 2]

[0037]
[Chemical Formula 3]

[0038]
[Formula 4]

[0039]
Considering the adhesion effect and desorption rate of the organic blue pigment, polysiloxane having a methylhydrogensiloxane unit, polyether-modified polysiloxane, and terminal carboxylic acid-modified polysiloxane having a terminal modified with a carboxylic acid are preferable.
[0040]
The coating amount of the organosilane compound or the polysiloxane is 0.02 to 5.0% by weight in terms of Si with respect to the organosilane compound-coated hydrous iron oxide particle powder or the polysiloxane-coated hydrous iron oxide particle powder. Is more preferable, 0.03 to 4.0% by weight, still more preferably 0.05 to 3.0% by weight.
[0041]
If it is less than 0.02% by weight, it is difficult to attach 5 parts by weight or more of the organic blue pigment to 100 parts by weight of the hydrous iron oxide powder.
[0042]
When the amount exceeds 5.0% by weight, 5 to 30 parts by weight of the organic blue pigment can be attached to 100 parts by weight of the hydrous iron oxide particle powder, so there is no meaning of covering more than necessary.
[0043]
The organic blue pigment in the present invention is a phthalocyanine pigment such as phthalocyanine blue, metal-free phthalocyanine blue, or fast sky blue, and alkali blue. Is preferred.
[0044]
The adhesion amount of the organic blue pigment is 5 to 30 parts by weight with respect to 100 parts by weight of the hydrous iron oxide powder.
[0045]
When the amount is less than 5 parts by weight or more than 30 parts by weight, it is difficult to obtain the green pigment targeted by the present invention. More preferably, it is 7.5-25 weight part.
[0046]
The particle shape and particle size of the green pigment according to the present invention greatly depend on the particle shape and particle size of the hydrous iron oxide particles as the core particles, and have a particle form similar to the core particles.
[0047]
That is, the green pigment according to the present invention has an average major axis diameter of 0.1 to 1.0 μm, preferably 0.15 to 0.9 μm.
[0048]
If the average major axis diameter of the green pigment exceeds 1.0 μm, the particle size is too large and the coloring power is reduced. When the average major axis diameter is less than 0.1 μm, aggregation is likely to occur due to an increase in intermolecular force due to particle miniaturization, so that dispersion in a vehicle or a resin composition becomes difficult.
[0049]
The green pigment according to the present invention has a needle shape or a rectangular parallelepiped shape.
[0050]
The green pigment according to the present invention preferably has an axial ratio of 20 or less, more preferably 2 to 15, and still more preferably 2 to 10. When the axial ratio exceeds 20, the particle entanglement increases, and the dispersibility in the vehicle or the resin composition may deteriorate or the viscosity may increase.
[0051]
The geometric standard deviation value of the major axis diameter of the green pigment is preferably 2.0 or less. If it exceeds 2.0, the coarse particles present make it difficult to uniformly disperse in the vehicle or resin composition. Considering uniform dispersion in the vehicle or resin composition, it is preferably 1.8 or less, more preferably 1.6 or less. Considering industrial productivity, the lower limit of the geometric standard deviation value of the particle size of the green pigment is 1.01, and those less than 1.01 are difficult to obtain industrially.
[0052]
The BET specific surface area value of the green pigment according to the present invention is 6 to 160 m.²/ G is preferable, more preferably 11 to 130 m.²/ G, even more preferably 16 to 110 m²/ G. BET specific surface area is 6m²If it is less than / g, since the green pigment is coarse, the coloring power is reduced. BET specific surface area is 160m²When the amount exceeds / g, aggregation tends to occur due to an increase in intermolecular force due to finer particles, so that dispersibility in a vehicle or a resin composition is lowered.
[0053]
The desorption rate of the organic blue pigment of the green pigment according to the present invention is preferably 15% or less, more preferably 12% or less. If the desorption rate of the organic blue pigment exceeds 15%, the desorbed organic blue pigment may inhibit uniform dispersion in the vehicle or resin composition, and the water content of the desorbed portion Since the hue of the iron oxide particle powder appears on the surface of the composite hydrous iron oxide particle powder, it is difficult to obtain a uniform hue.
[0054]
The hue of the green pigment according to the present invention is L^*Value is 25-80, a^*Value is -100 ≦ a^*Value <0, b^*The value is -100 ≦ b^*Values ≦ + 100 and h values are in the range of 120 ° ≦ h value ≦ 240 °.
[0055]
The heat resistance of the green pigment according to the present invention is improved by +5 to + 40 ° C. with respect to the heat resistance temperature of the hydrous iron oxide particle powder which is a particle powder.
[0056]
The coloring power of the green pigment according to the present invention is preferably 115% or more, more preferably 120% or more, in the evaluation method described later.
[0057]
The hiding power of the green pigment according to the present invention is 1,750 cm by an evaluation method described later.²/ G or more, more preferably 1,800 cm²/ G or more.
[0058]
The chemical resistance of the green pigment according to the present invention is an evaluation method described later, and the acid resistance is ΔE.^*The value is preferably 1.5 or less, more preferably 1.2 or less, and the alkali resistance is ΔE.^*The value is preferably 1.5 or less, more preferably 1.2 or less.
[0059]
The green pigment according to the present invention, if necessary, at least one kind selected from a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon in advance on the particle surface of the hydrous iron oxide powder. It may be coated with an intermediate coating consisting of the above, and the detachment of the organic blue pigment from the particle surface of the hydrous iron oxide particle powder can be further reduced as compared with the case where it is not coated with the intermediate coating. , Heat resistance is improved.
[0060]
The coating amount by the intermediate coating is Al equivalent to the hydrated iron oxide particle powder coated with the intermediate coating, SiO₂Conversion or Al conversion amount and SiO₂The total amount with the converted amount is preferably 0.01 to 20% by weight.
[0061]
If it is less than 0.01% by weight, the effect of reducing the desorption rate of the organic blue pigment cannot be obtained. Since the effect of reducing the desorption rate of the organic blue pigment can be sufficiently obtained with a coating amount of 0.01 to 20% by weight, there is no point in covering more than 20% by weight.
[0062]
The green pigment according to the present invention coated with an intermediate coating has almost the same particle size, geometric standard deviation value, BET specific surface area as the green pigment according to the present invention not coated with an intermediate coating. Value, hue (L^*Value, a^*Value, b^*Value, h value), coloring power, hiding power and chemical resistance. Further, the desorption rate of the green pigment is improved by coating the intermediate coating, and the desorption rate is preferably 12% or less, more preferably 10% or less. Moreover, heat resistance improves about + 5- + 30 degreeC with respect to the green pigment using the core particle powder which does not contain aluminum.
[0063]
Next, a paint containing the green pigment according to the present invention will be described.
[0064]
The paint blended with the green pigment according to the present invention has a storage stability of ΔE.^*The value is preferably 1.5 or less, more preferably 1.2 or less. When a coating film is used, the glossiness is 75 to 110%, preferably 80 to 110%, the heat resistance temperature of the coating film is 240 ° C. or higher, preferably 245 ° C. or higher. The ΔG value is preferably 12% or less, more preferably 10% or less, and the alkali resistance is preferably a ΔG value of 12% or less, more preferably 10% or less, and the hue is L^*Value is 25-85, a^*Value is -100 ≦ a^*Value <0, b^*The value is -100 ≦ b^*The value ≦ + 100 and the h value are preferably 120 ° ≦ h value ≦ 240 °.
[0065]
The paint blended with the green pigment having the particle surface according to the present invention coated with an intermediate coating has a storage stability of ΔE.^*The value is preferably 1.5 or less, more preferably 1.2 or less. When the coating film is used, the glossiness is 80 to 115%, preferably 85 to 115%, the heat resistance temperature of the coating film is 245 ° C. or higher, preferably 250 ° C. or higher. The ΔG value is preferably 12% or less, more preferably 10% or less, and the alkali resistance is preferably ΔG value of 12% or less, more preferably 10% or less, and the hue is L^*Value is 25-85, a^*Value is -100 ≦ a^*Value <0, b^*The value is -100 ≦ b^*The value ≦ + 100 and the h value are preferably 120 ° ≦ h value ≦ 240 °.
[0066]
The water-based paint containing the green pigment according to the present invention has a storage stability of ΔE.^*The value is preferably 1.5 or less, more preferably 1.2 or less. When a coating film is used, the glossiness is 70 to 110%, preferably 75 to 110%, the heat resistance temperature of the coating film is 235 ° C. or higher, preferably 240 ° C. or higher. The ΔG value is preferably 12% or less, more preferably 10% or less, and the alkali resistance is preferably a ΔG value of 12% or less, more preferably 10% or less, and the hue is L^*Value is 25-85, a^*Value is -100 ≦ a^*Value <0, b^*The value is -100 ≦ b^*The value ≦ + 100 and the h value are preferably 120 ° ≦ h value ≦ 240 °.
[0067]
The water-based paint blended with the green pigment whose particle surface is coated with an intermediate coating according to the present invention has a storage stability of ΔE of 1.5 or less, more preferably 1.2 or less. When the coating film is used, the glossiness is 75 to 115%, preferably 80 to 115%, the heat resistance temperature of the coating film is 240 ° C. or higher, preferably 245 ° C. or higher. The ΔG value is preferably 12% or less, more preferably 10% or less, and the alkali resistance is preferably ΔG value of 12% or less, more preferably 10% or less, and the hue is L^*Value is 25-85, a^*Value is -100 ≦ a^*Value <0, b^*The value is -100 ≦ b^*The value ≦ + 100 and the h value are preferably 120 ° ≦ h value ≦ 240 °.
[0068]
The blending ratio of the green pigment in the paint according to the present invention can be used in the range of 1.0 to 100 parts by weight with respect to 100 parts by weight of the base material constituting the paint, and preferably considering the handling of the paint It is 2.0-100 weight part, More preferably, it is 5.0-100 weight part.
[0069]
As the coating material constituting substrate, a resin, a solvent, and if necessary, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are blended.
[0070]
As the resin, acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin and the like that are usually used for solvent-based paints can be used. For water-based paints, commonly used water-soluble alkyd resins, water-soluble melamine resins, water-soluble acrylic resins, water-soluble urethane emulsion resins and the like can be used.
[0071]
As the solvent, toluene, xylene, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, aliphatic hydrocarbons and the like that are usually used for solvent-based paints can be used.
[0072]
As a solvent for water-based paints, water and butyl cellosolve, butyl alcohol or the like usually used in water-based paints can be mixed and used.
[0073]
Antifoaming agents include Nopco 8034 (product name), SN deformer 477 (product name), SN deformer 5013 (product name), SN deformer 247 (product name), SN deformer 382 (product name) (all of these are San Nopco Commercially available products such as manufactured by Co., Ltd., Antihome 08 (trade name), Emulgen 903 (trade name) (all of which are manufactured by Kao Corporation) can be used.
[0074]
Next, a resin composition colored with the green pigment according to the present invention will be described.
[0075]
The resin composition colored with the green pigment according to the present invention has a dispersion state by visual observation of 4 or 5, preferably 5, according to the later evaluation method, and the heat resistance temperature of the resin composition is 215 ° C. or higher. Preferably it is 220 degreeC or more, and a hue is L^*Value is 25-85, a^*Value is -100 ≦ a^*Value <0, b^*The value is -100 ≦ b^*The value ≦ + 100 and the h value are preferably 120 ° ≦ h value ≦ 240 °.
[0076]
The resin composition colored with the green pigment having the particle surface according to the present invention coated with an intermediate coating has a dispersion state by visual observation of 4 or 5, preferably 5, according to the later evaluation method. The heat-resistant temperature of the composition is 220 ° C. or higher, preferably 225 ° C. or higher, and the hue is L^*Value is 25-85, a^*Value is -100 ≦ a^*Value <0, b^*The value is -100 ≦ b^*The value ≦ + 100 and the h value are preferably 120 ° ≦ h value ≦ 240 °.
[0077]
The blending ratio of the green pigment in the resin composition according to the present invention can be used in the range of 0.5 to 200 parts by weight with respect to 100 parts by weight of the resin, and preferably considering the handling of the resin composition Is 1.0 to 150 parts by weight, more preferably 2.5 to 100 parts by weight.
[0078]
As a constituent substrate in the resin composition according to the present invention, additives such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers are blended as necessary together with a green pigment and a known thermoplastic resin. Is done.
[0079]
As the resin, natural rubber, synthetic rubber, thermoplastic resin (for example, polyolefin such as polyethylene, polypropylene, polybutene, polyisobutylene, polyvinyl chloride, styrene polymer, polyamide, etc.) can be used.
[0080]
The amount of the additive may be 50% by weight or less based on the total amount of the green pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.
[0081]
In the resin composition according to the present invention, the resin raw material and the green pigment are mixed well in advance, and then a strong shearing action is applied under heating using a kneader or an extruder to destroy the aggregate of the green pigment. Then, after the green pigment is uniformly dispersed in the resin composition, it is molded into a shape suitable for the purpose and used.
[0082]
Next, a method for producing the green pigment according to the present invention will be described.
[0083]
The green pigment according to the present invention is a mixture of hydrous iron oxide powder and alkoxysilane or polysiloxane, and the surface of the hydrous iron oxide powder is coated with alkoxysilane or polysiloxane, and then with alkoxysilane or polysiloxane. It can be obtained by mixing the coated hydrous iron oxide powder and the organic blue pigment.
[0084]
Coating the surface of the hydrous iron oxide particle powder with the alkoxysilane or polysiloxane is performed by mechanically mixing and stirring the hydrous iron oxide particle powder and the alkoxysilane solution or polysiloxane, or by adding the alkoxysilane to the hydrous iron oxide particle powder. Alternatively, mechanical mixing and stirring may be performed while spraying polysiloxane. Almost all of the added alkoxysilane or polysiloxane is coated on the particle surface of the hydrous iron oxide particle powder.
[0085]
In addition, the coated alkoxysilane may be coated as an organosilane compound generated from alkoxysilane, a part of which is generated through a coating process. Even in this case, the subsequent adhesion of the organic blue pigment is not affected.
[0086]
In order to coat the alkoxysilane or polysiloxane uniformly on the surface of the hydrous iron oxide particle powder, it is preferable that the coagulation of the hydrous iron oxide particle powder is previously unraveled using a pulverizer.
[0087]
Equipment for mixing and stirring the core particle powder and alkoxysilane or polysiloxane, and mixing and stirring the organic blue pigment and the core particle powder coated with an organosilane compound or polysiloxane generated from alkoxysilane on the particle surface Is preferably a device capable of applying a shear force to the powder layer, in particular, a device capable of simultaneously performing shearing, spatula and compression, such as a wheel-type kneader, a ball-type kneader, a blade-type kneader, A roll-type kneader can be used. In carrying out the present invention, a wheel-type kneader can be used more effectively.
[0088]
Specific examples of the wheel type kneader include edge runners (synonymous with “mix muller”, “simpson mill”, “sand mill”), multi-mal, stotz mill, wet pan mill, conner mill, ring muller, and the like. , Preferably an edge runner, multi-mal, Stots mill, wet pan mill, and ring muller, and more preferably an edge runner. Specific examples of the ball kneader include a vibration mill. Specific examples of the blade-type kneader include a Henschel mixer, a planetary mixer, and a nauta mixer. Specific examples of the roll-type kneader include an extruder.
[0089]
The conditions during mixing and stirring are such that the linear load is 19.6 to 1960 N / cm (2 to 200 Kg / cm), preferably so that the alkoxysilane or polysiloxane is coated as uniformly as possible on the surface of the hydrous iron oxide powder. Is 98 to 1470 N / cm (10 to 150 Kg / cm), more preferably 147 to 980 N / cm (15 to 100 Kg / cm), and the treatment time is 5 to 120 minutes, preferably 10 to 90 minutes. What is necessary is just to adjust suitably. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.
[0090]
The amount of alkoxysilane or polysiloxane added is preferably 0.15 to 45 parts by weight with respect to 100 parts by weight of the hydrous iron oxide particle powder. When the amount is less than 0.15 parts by weight, it is difficult to attach an organic blue pigment sufficient to obtain the target green pigment. The addition amount of 0.15 to 45 parts by weight makes it possible to attach 5 to 30 parts by weight of the organic blue pigment with respect to 100 parts by weight of the hydrous iron oxide powder. There is no meaning to do.
[0091]
Next, the organic blue pigment is added to the hydrous iron oxide powder coated with alkoxysilane or polysiloxane, and mixed and stirred to adhere the organic blue pigment to the alkoxysilane coating or polysiloxane coating. If necessary, drying or heat treatment may be further performed.
[0092]
The organic blue pigment is preferably added in small portions over time, particularly over about 5 to 60 minutes.
[0093]
The conditions during mixing and stirring are such that the linear load is 19.6 to 1960 N / cm (2 to 200 Kg / cm), preferably 98 to 1470 N / cm (10 to 150 Kg / cm) so that the organic blue pigment adheres uniformly. More preferably, the processing conditions may be appropriately adjusted within the range of 147 to 980 N / cm (15 to 100 Kg / cm) and the processing time of 5 to 120 minutes, preferably 10 to 90 minutes. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.
[0094]
The addition amount of the organic blue pigment is 5 to 30 parts by weight with respect to 100 parts by weight of the hydrous iron oxide particle powder. If the amount of organic blue pigment added is outside the above range, the desired green pigment cannot be obtained.
[0095]
The heating temperature in the drying or heating step is usually preferably 40 to 200 ° C, more preferably 60 to 150 ° C. The treatment time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours.
[0096]
The hydrous iron oxide powder is, if necessary, at least selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide prior to mixing and stirring with alkoxysilane or polysiloxane. You may coat | cover with the intermediate coating which consists of 1 type.
[0097]
Coating with an intermediate coating is performed by adding an aluminum compound, a silicon compound, or both of these compounds to an aqueous suspension obtained by dispersing hydrous iron oxide powder and mixing and stirring, or if necessary, mixing and stirring. An intermediate coating consisting of at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide, by adjusting the pH value later. And then filter, wash, dry and grind. If necessary, a deaeration / consolidation process may be further performed.
[0098]
As the aluminum compound, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride, and aluminum nitrate, and alkali aluminates such as sodium aluminate can be used.
[0099]
As the silicon compound, No. 3 water glass, sodium orthosilicate, sodium metasilicate and the like can be used.
[0100]
DETAILED DESCRIPTION OF THE INVENTION
A typical embodiment of the present invention is as follows.
[0101]
The average major axis diameter and average minor axis diameter of the particles were measured by measuring the major axis diameter and minor axis diameter of 350 particles shown in the photograph obtained by enlarging the electron micrograph four times in the vertical and horizontal directions, respectively. The average value is shown.
[0102]
The axial ratio is shown as the ratio of the average major axis diameter to the average minor axis diameter.
[0103]
The particle size distribution of the major axis diameter of the particles is shown by the value obtained by the following method.
[0104]
That is, the value measured for the major axis diameter of the particles shown in the above enlarged photograph is calculated on the basis of the actual major axis diameter and the number of particles calculated from the measured value, and the horizontal axis on the lognormal probability paper according to a statistical method. The long axis diameter is plotted on the vertical axis, and the cumulative number of particles belonging to each of the predetermined long axis diameter sections (under the integrated sieve) is plotted in percentage on the vertical axis. Then, the value of the major axis diameter corresponding to the number of particles of 50% and 84.13% is read from this graph, and the geometrical standard deviation value = major axis diameter under integrated fluid under 84.13% / under integrated fluid under 50. The value was calculated according to the major axis diameter (geometric mean diameter) in%. The closer the geometric standard deviation value is to 1, the better the particle size distribution of the particles.
[0105]
The specific surface area value was indicated by a value measured by the BET method.
[0106]
Each of the amount of Al present in the particles and the surface of the particles of the hydrous iron oxide powder and the green pigment, the amount of Si, and the amount of Si contained in the organosilane compound or polysiloxane produced from the alkoxysilane is “fluorescence. Using an “X-ray analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.), the measurement was performed in accordance with “General X-ray fluorescence analysis rules” of JIS K0119.
[0107]
In addition, each Si of Si contained in the organosilane compound produced | generated from the oxide of silicon which coat | covers the particle | grain surface of a hydrous iron oxide particle powder, a hydroxide of silicon, and an alkoxysilane, or polysiloxane The amount was shown as a value obtained by measuring the Si amount at each stage after the treatment process and subtracting the Si amount measured at the stage before the treatment process from the measured value.
[0108]
The coating amount of the organic blue pigment adhering to the green pigment was determined by measuring the carbon amount using “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 Model” (manufactured by Horiba, Ltd.).
[0109]
The desorption rate (%) of the organic blue pigment adhering to the green pigment was indicated by the value obtained by the following method. The closer the organic blue pigment detachment rate is to 0%, the smaller the amount of organic blue pigment detachment from the green pigment particle surface.
[0110]
3 g of the green pigment and 40 ml of ethanol were placed in a 50 ml sedimentation tube, subjected to ultrasonic dispersion for 20 minutes, and then allowed to stand for 120 minutes to separate the green pigment from the detached organic blue pigment by the sedimentation speed. Next, 40 ml of ethanol was again added to the green pigment, and after ultrasonic dispersion for 20 minutes, the mixture was allowed to stand for 120 minutes to separate the green pigment from the detached organic blue pigment. This green pigment was dried at 80 ° C. for 1 hour, the amount of the organic blue pigment was measured, and the value obtained according to the following formula 1 was taken as the desorption rate (%) of the organic blue pigment.
[0111]
[Expression 1]
Desorption rate of organic blue pigment (%) = {(Wa-We) / Wa} × 100
Wa: Organic blue pigment adhesion amount of green pigment
We: Green blue pigment organic blue pigment adhesion after desorption test
[0112]
The hues of the hydrous iron oxide powder and the green pigment are paste-like by kneading 0.5 g of the sample and 0.5 ml of castor oil with a Hoover-type Mahler, and adding 4.5 g of clear lacquer to this paste to knead and paint. An application piece (coating thickness: about 30 μm) coated on a cast-coated paper using a 150 μm (6 mil) applicator was prepared, and a multi-light source spectrocolorimeter (MSC-IS-2D, Suga test) was applied to the coated piece. Machine-made) L using Multi-spctro-color-Meter^*Value, a^*Value and b^*The value was measured.
[0113]
In addition, h value is a obtained by the said measurement.^*Value and b^*Using the value, it can be obtained according to the following formula 2.
[0114]
[Expression 2]
h = tan^-1(B^*/ A^*(A^*> 0, b^*≤ 0)
h = 180 + tan^-1(B^*/ A^*(A^*<If 0)
h = 360 + tan^-1(B^*/ A^*(A^*> 0, b^*<If 0)
[0115]
The heat resistance of the green pigment is measured by differential scanning calorimetry (DSC) of the measured particle powder using a thermal analyzer SSC5000 (manufactured by Seiko Denshi Kogyo Co., Ltd.), and the peak shown on the obtained DSC chart is shown. Of the two inflection points to be formed, a tangent line was drawn for each of the two curves constituting the first inflection point, and the temperature corresponding to the intersection of both tangent lines was read and indicated by that temperature.
[0116]
The coloring power of the hydrous iron oxide particle powder, organic blue pigment and green pigment was applied by applying each of the primary color enamel and the color development enamel prepared according to the method shown below onto a cast coated paper using a 150 μm (6 mil) applicator. An application piece is prepared, and the application piece is subjected to L using a multi-light spectrocolorimeter (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-spctro-color-Meter.^*Measure the value and the difference is ΔL^*ΔLs of chromium green (Comparative Example 6) used as a standard sample^*The value calculated according to the following formula 3 using the value was shown as coloring power (%).
[0117]
[Equation 3]
Coloring power (%) = 100 + {(ΔLs^*-ΔL^*) × 10}
[0118]
Production of primary color enamel:
10 g of the above sample powder, 16 g of amino alkyd resin and 6 g of thinner were mixed and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed for 45 minutes with a paint shaker, and then 50 g of amino alkyd resin was added. Further, it was dispersed with a paint shaker for 5 minutes to produce a primary color enamel.
[0119]
Production of color-enamel:
12 g of the primary color enamel and 40 g of amylac white (titanium dioxide-dispersed aminoalkyd resin) were blended and mixed and dispersed for 15 minutes with a paint shaker to produce a color-enamel.
[0120]
The hiding power of the hydrous iron oxide powder, the organic blue pigment, and the green pigment was represented by the value obtained according to the cryptometer method of JIS K 5101 8.2 using the primary color enamel obtained above.
[0121]
The acid resistance of the hydrous iron oxide particle powder, the organic blue pigment, and the green pigment was determined by immersing 10 g of the sample powder in 5% sulfuric acid for 10 minutes, then removing the sample from the sulfuric acid aqueous solution, washing it with water, and drying. A coating film is prepared in the same manner as in^*Value, a^*Value and b^*The color difference ΔE measured according to the following equation 4^*Indicated by value. ΔE^*It shows that it is excellent in acid resistance, so that a value is small.
[0122]
The alkali resistance of the hydrous iron oxide particle powder, the organic blue pigment and the green pigment is obtained by immersing 10 g of the sample powder in a 1% aqueous solution of caustic soda for 15 minutes, and then removing the sample from the aqueous solution of caustic soda, washing it and drying it. A coating film is prepared by the same method as described above, and L^*Value, a^*Value and b^*The color difference ΔE measured according to the following equation 4^*Indicated by value. ΔE^*It shows that it is excellent in alkali resistance, so that a value is small.
[0123]
[Expression 4]
ΔE^*Value = ((ΔL^*)²+ (Δa^*)²+ (Δb^*)²)^1/2
ΔL^*Value: L before and after immersion of acid or alkali in sample powder^*Difference in values
Δa^*Value: a before and after acid or alkali immersion treatment of sample powder^*Difference in values
Δb^*Value: b before and after acid or alkali immersion treatment of sample powder^*Difference in values
[0124]
The hue of each coating film of the solvent-based paint and water-based paint obtained using the green pigment is a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) The hue of the resin composition colored with a green pigment was prepared by the method described later using a coating piece for measurement obtained by coating and drying to a thickness of 150 μm to form a coating film. Using a colored resin plate, the coated piece and the plate were respectively separated using a multi-light source spectrocolorimeter (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-spctro-color-Meter.^*Value, a^*Value and b^*The value was measured.
[0125]
In addition, h value is a obtained by the said measurement.^*Value and b^*Using the measurement of the value, it was determined according to the above formula 2.
[0126]
The glossiness of the coating film was represented by the glossiness when the incident angle was 60 ° using the “Glossmeter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.). It shows that the dispersibility of the coating material which mix | blended the green pigment is excellent, so that glossiness is high.
[0127]
The heat resistance of the coating film using the green pigment is determined by placing the measurement application piece in an electric furnace, performing various heat treatments for 15 minutes at various temperatures, and heating the application piece at each temperature. Hue before and after (L^*Value, a^*Value, b^*Value) is measured using a multi-light source spectrocolorimeter (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-sptro-color-Meter, and the following formula 5 based on the colorimetric values before heating: ΔE indicated^*Using a semi-log graph, the horizontal axis represents the heating temperature and the vertical axis represents ΔE^*Plot the values and ΔE^*The temperature at which the value was just 1.5 was defined as the heat resistant temperature of the coating film.
[0128]
[Equation 5]
ΔE^*Value = ((ΔL^*value)²+ (Δa^*value)²+ (Δb^*value)²)^1/2
ΔL^*Value: L before and after heat treatment of the coating film to be compared^*Difference in values
Δa^*Value: a before and after heat treatment of the coating film to be compared^*Difference in values
Δb^*Value: b before and after heat treatment of the coating film to be compared^*Difference in values
[0129]
The storage stability of the paint obtained using the green pigment is determined by blending the prescribed composition described below in a prescribed ratio and dispersing the mill base for 90 minutes. * 70mm * 150mm) (JIS-G-3141) with a thickness of 150 [mu] m applied and dried to produce a coating color L^*Value, a^*Value and b^*The value and the hue of a coating film produced by applying the coating material obtained by allowing the coating material to stand at 25 ° C. for 1 week on a cold-rolled steel sheet and drying it were measured.^*Indicated by value.
[0130]
[Formula 6]
ΔE^*Value = ((ΔL^*)²+ (Δa^*)²+ (Δb^*)²)^1/2
ΔL^*Value: L before and after standing of the coating film to be compared^*Difference in values
Δa^*Value: a before and after standing of the coating film to be compared^*Difference in values
Δb^*Value: b before and after standing of the coating film to be compared^*Difference in values
[0131]
The acid resistance of the coating film is a thickness of 150 μm on a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm: JIS G-3141) obtained by blending the following predetermined composition with a predetermined ratio. A sample having a coating film produced by coating and drying is prepared, and the glossiness is measured. Next, a 5% by weight sulfuric acid aqueous solution is placed in a 1000 ml beaker, the coated piece is hung with a thread, immersed to a depth of about 120 mm, and left at 25 ° C. for 24 hours.
[0132]
Next, the coated piece is taken out of the sulfuric acid aqueous solution, gently washed with running water, shaken off the water, and then the glossiness of the central portion of the coated piece is measured. And the glossiness change ((DELTA) G value) before and behind immersion in sulfuric acid aqueous solution was measured, and acid resistance was evaluated by the magnitude | size. It shows that it is excellent in acid resistance, so that (DELTA) G value is small.
[0133]
The alkali resistance of the coating film is a thickness of 150 μm on a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm: JIS G-3141) obtained by blending the following predetermined composition with a predetermined ratio. A sample having a coating film produced by coating and drying is prepared, and the glossiness is measured. Next, a 1% sodium hydroxide aqueous solution is put into a 1000 ml beaker, the above-mentioned coated piece is hung with a thread, immersed to a depth of about 120 mm, and allowed to stand at 25 ° C. for 24 hours.
[0134]
Next, the coated piece is taken out from the aqueous caustic soda solution and gently washed with running water. After the water has been shaken off, the glossiness of the central portion of the coated piece is measured. And the glossiness change ((DELTA) G value) before and behind immersion in sulfuric acid aqueous solution was measured, and alkali resistance was evaluated by the magnitude | size.
It shows that it is excellent in alkali resistance, so that (DELTA) G value is small.
[0135]
The heat resistance of the resin composition colored using a green pigment is obtained by cutting a colored resin plate prepared according to a formulation described later into 5 cm square, subjecting the colored resin plate to hot pressing, and changing the hot pressing temperature in various ways. 98 MPa (1 ton / cm at each temperature)²) Is applied for 10 minutes while applying the load, and the color of the colored resin plate before and after heating at each temperature (L^*Value, a^*Value, b^*Value) was measured using a multi-light source spectrocolorimeter (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-spctro-color-Meter, and represented by the following formula 7 based on the colorimetric values before heating. ΔE^*Using a semi-log graph, the horizontal axis represents the heating temperature and the vertical axis represents ΔE^*Plot the values and ΔE^*The temperature at which the value was just 1.5 was defined as the heat resistant temperature of the resin composition.
[0136]
[Expression 7]
ΔE^*Value = ((ΔL^*value)²+ (Δa^*value)²+ (Δb^*value)²)^1/2
ΔL^*Value: L before and after heat treatment of colored resin plates to be compared^*Difference in values
Δa^*Value: a before and after heat treatment of colored resin plates to be compared^*Difference in values
Δb^*Value: b before and after heat treatment of colored resin plates to be compared^*Difference in values
[0137]
Regarding the paint viscosity, the paint viscosity at 25 ° C. of the paint prepared according to the formulation described below is measured by using an E type viscometer (cone plate type viscometer) EMD-R (manufactured by Tokyo Keiki Co., Ltd.) and a shear rate D = 1. .92 sec^-1The value at was determined.
[0138]
The dispersibility of the green pigment in the resin composition was evaluated in five stages by visually determining the number of undispersed aggregated particles on the surface of the obtained colored resin plate. 5 indicates the best dispersion state.
5: Undispersed material is not recognized,
4: 1cm²1 to less than 5,
3: 1 cm²5 to less than 10 per,
2: 1 cm²10 to less than 50 per,
1: 1cm²More than 50 per.
[0139]
<Manufacture of green pigments>
Goethite particle powder (particle shape: needle shape, average major axis diameter 0.40 μm, axial ratio 5.3, geometric standard deviation value 1.44, BET specific surface area value 18.8 m²/ G, L^*Value 59.3, a^*Value 16.5, b^*13.0 kg of the value 53.9, h value 73.0 °, heat resistance 198 ° C.) was added to the edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Foundry Co., Ltd.), and methyltriethoxysilane ( (Product name: TSL8123: manufactured by Toshiba Silicone Co., Ltd.) A methyltriethoxysilane solution obtained by mixing and diluting 220 g with 200 ml of ethanol was added to the above goethite particle powder while operating an edge runner, and 392 N / cm (40 Kg / cm) and mixed and stirred for 20 minutes. The stirring speed at this time was 22 rpm.
[0140]
Next, organic blue pigment A (type: phthalocyanine blue, particle shape: granular, average major axis diameter 0.06 μm, hiding power 240 cm²/ G, L^*Value 17.7, a^*Value 9.7, b^*Value-23.4, h value 292.5 °, heat resistance 256 ° C.) 825 g was added over 10 minutes while running the edge runner, and further for 20 minutes with a linear load of 392 N / cm (40 Kg / cm), After mixing and stirring to deposit the organic blue pigment A on the methyltriethoxysilane coating, a heat treatment was performed at 105 ° C. for 60 minutes using a dryer to obtain a green pigment. The stirring speed at this time was 22 rpm.
[0141]
The obtained green pigment was a needle-like particle powder having an average major axis diameter of 0.40 μm and an axial ratio of 5.3. Geometric standard deviation value is 1.44, BET specific surface area value is 20.1m²/ G, L^*The value is 39.9, a^*Values are -13.2, b^*Value is +19.8, h value is 123.7 °, coloring power is 141%, hiding power is 1,950 cm²/ G, out of chemical resistance, acid resistance is ΔE^*Value of 0.99, alkali resistance is ΔE^*The value is 0.86, the heat resistance is 227 ° C., the desorption rate of the organic blue pigment is 7.0%, and the coating amount of the organosilane compound formed from methyltriethoxysilane is 0.29 weight in terms of Si. %, The amount of adhering organic blue pigment was 4.61% by weight in terms of C (corresponding to 7.5 parts by weight with respect to 100 parts by weight of goethite particle powder).
[0142]
As a result of observing an electron micrograph, since almost no organic blue pigment was observed, it was confirmed that almost all of the organic blue pigment adhered to the organosilane compound coating formed from methyltriethoxysilane.
[0143]
<Manufacture of solvent-based paints containing green pigments>
10 g of the green pigment, aminoalkyd resin and thinner were blended in the following proportions and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed for 90 minutes with a paint shaker to prepare a mill base.
[0144]
Green pigment 12.2 parts by weight,
19.5 parts by weight of amino alkyd resin,
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
Thinner 7.3 parts by weight.
[0145]
Using the mill base, an amino alkyd resin was blended so as to have the following ratio, and further mixed and dispersed for 15 minutes with a paint shaker to obtain a solvent-based paint containing a green pigment.
[0146]
39.0 parts by weight of mill base,
Aminoalkyd resin 61.0 parts by weight.
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
[0147]
The solvent-based paint obtained has a paint viscosity of 1,452 cP, and the paint storage stability is ΔE.^*The value was 0.92.
[0148]
Next, the gloss of the coating film obtained by applying the solvent-based coating to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 87%, The heat-resistant temperature is 249 ° C and the hue is L^*The value is 40.2, a^*The value is -12.4, b^*The value was +20.5, the h value was 121.2 °, the acid resistance was 9.3% in terms of ΔG value, and the alkali resistance was 7.9% in terms of ΔG value.
[0149]
<Manufacture of water-based paints containing green pigments>
The above-mentioned green pigment 7.62 g and water-soluble alkyd resin and the like were added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads in the following ratio, and then mixed and dispersed for 90 minutes with a paint shaker to prepare a mill base.
[0150]
12.4 parts by weight of a green pigment,
9.0 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
4.8 parts by weight of water,
Butyl cellosolve 4.1 parts by weight.
[0151]
Using the mill base, the coating composition was blended at the following ratio, and further mixed and dispersed for 15 minutes with a paint shaker to obtain a water-soluble coating.
[0152]
30.4 parts by weight of mill base,
46.2 parts by weight of a water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
12.6 parts by weight of a water-soluble melamine resin,
(Product name: S-695: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
9.1 parts by weight of water,
Butyl cellosolve 1.6 parts by weight.
[0153]
The resulting water-based paint has a paint viscosity of 2,118 cP and a storage stability of ΔE.^*The value was 1.00.
[0154]
Next, the gloss of the coating film obtained by applying the above water-based paint to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 82%. Heat-resistant temperature is 247 ° C, hue is L^*The value is 40.7, a^*The value is -12.6, b^*The value was +20.9, h value was 121.1 °, acid resistance was 9.6% in ΔG value, and alkali resistance was 8.8% in ΔG value.
[0155]
<Manufacture of resin composition>
The green pigment 2.5 g and polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.) 47.5 g were weighed, put in a 100 ml poly beaker and mixed well with a spatula to obtain a mixed powder.
[0156]
After adding 0.5 g of calcium stearate to the obtained mixed powder and mixing, and setting the clearance of a hot roll heated to 160 ° C. to 0.2 mm, the above mixed powder is kneaded with a roll little by little to obtain a resin composition The kneading was continued until the products were integrated, and then the resin composition was peeled from the roll and used as a colored resin plate raw material.
[0157]
Next, the resin composition is sandwiched between surface-polished stainless steel plates and placed in a hot press heated to 180 ° C. 1 ton / cm²And a colored resin plate having a thickness of 1 mm was obtained. The dispersion state of the obtained colored resin plate is 5, the heat resistance temperature of the colored resin plate is 223 ° C., and the hue is L^*The value is 42.2, a^*The value is -10.8, b^*The value was +17.9, and the h value was 121.1 °.
[0158]
[Action]
The most important point in the present invention is that the particle surface of the hydrated iron oxide particle powder is coated with an organosilane compound or polysiloxane generated from alkoxysilane, and an organic blue pigment is attached to the coating. Is the fact that it is a harmless green pigment with excellent chemical resistance, high hiding power and coloring power, and improved heat resistance.
[0159]
The reason why a pigment exhibiting a green color is obtained in the present invention is the same principle as that when a blue transparent film is superimposed on a yellow film, and the hydrous iron oxide particle powder exhibiting a yellow color with an organic blue pigment having a low hiding power. It is considered that it looks green when covered.
[0160]
The reason why the green pigment according to the present invention is excellent in chemical resistance is that the hydrous iron oxide powder as the core particle powder is excellent in chemical resistance, and the organic blue pigment adhered to the particle powder is also It is considered that the chemical resistance of the whole particle is further improved by selecting one having excellent chemical resistance.
[0161]
The reason why the green pigment according to the present invention is excellent in hiding power and coloring power is that the surface of the hydrous iron oxide powder having excellent hiding power and coloring power is coated with an organic blue pigment via an organosilane compound or polysiloxane coating. It is considered that a pigment having excellent hiding power and coloring power can be obtained by being firmly fixed and combined.
[0162]
The reason why the heat resistance of the green pigment according to the present invention is excellent is that the hydrous iron oxide particle powder originally inferior in heat resistance is coated with an organosilane compound or polysiloxane excellent in heat resistance, and further excellent in heat resistance. It is considered that the heat resistance as a green pigment is improved by fixing the organic blue pigment.
[0163]
The green pigment according to the present invention does not contain harmful elements and compounds, so it is excellent in hygiene and safety, and is a pigment that takes environmental pollution into consideration.
[0164]
【Example】
Next, examples and comparative examples are shown.
[0165]
Core particles 1 to 4:
As the core particle powder, a hydrous iron oxide particle powder having the characteristics shown in Table 1 was prepared.
[0166]
[Table 1]

[0167]
Core particle 5:
Using 20 kg of acicular goethite particle powder of core particle 1 and 150 l of water, a slurry containing acicular goethite particle powder was obtained. The pH value of the redispersed slurry containing the obtained acicular goethite particle powder was adjusted to 10.5 using an aqueous sodium hydroxide solution, and then water was added to the slurry to adjust the slurry concentration to 98 g / l. 150 l of this slurry was heated to 60 ° C., and 2722 ml of a 1.0 mol / l sodium aluminate solution (corresponding to 0.5% by weight in terms of Al with respect to acicular goethite particle powder) was added to the slurry, After holding for 30 minutes, the pH value was adjusted to 7.5 using acetic acid. After maintaining for 30 minutes in this state, filtration, washing with water, drying, and pulverization yielded acicular goethite particle powders whose particle surfaces were coated with aluminum hydroxide.
[0168]
The production conditions at this time are shown in Table 2, and the properties of the obtained surface-treated goethite particle powder are shown in Table 3.
[0169]
Core particles 6-8:
Hydroxic oxide in which the particle surface is coated with a coating in the same manner as the core particle 5 except that each hydrous iron oxide powder of core particles 2 to 4 is used and the type and amount of the surface coating are variously changed. An iron particle powder was obtained.
[0170]
The production conditions at this time are shown in Table 2, and the properties of the surface-treated hydrous iron oxide particles obtained are shown in Table 3.
[0171]
[Table 2]

[0172]
[Table 3]

[0173]
In the surface treatment step, the type of coating A is an aluminum hydroxide, and S represents a silicon oxide.
[0174]
Organic blue pigment A, B:
As an organic blue pigment, phthalocyanine blue having various characteristics shown in Table 4 was prepared.
[0175]
[Table 4]

[0176]
Examples 1-8, Comparative Examples 1-5:
Types and amounts of additives in the coating process with alkoxysilane, polysiloxane, and silicon compound, line load and time for edge runner treatment, types and amounts of organic blue pigment in the adhesion process of organic blue pigment, lines for edge runner treatment A green pigment was obtained in the same manner as in the above embodiment except that the load and time were variously changed.
[0177]
The production conditions at this time are shown in Table 5, and various characteristics of the obtained green pigment are shown in Table 6.
[0178]
Comparative Examples 6-8
Table 6 shows properties of chromium green as Comparative Example 6, chromium oxide as Comparative Example 7, and phthalocyanine green as Comparative Example 8 alone.
[0179]
[Table 5]

[0180]
[Table 6]

[0181]
Examples 9-16, Comparative Examples 9-16:
A paint was obtained in the same manner as in the above embodiment except that the type of the green pigment was changed variously.
[0182]
Table 7 shows various properties of the obtained paint and various properties of the coating film.
[0183]
[Table 7]

[0184]
Examples 17-24, Comparative Examples 17-24:
A water-based paint was obtained in the same manner as in the above-described embodiment except that the type of the green pigment was variously changed.
[0185]
Table 8 shows various characteristics of the obtained water-based paint and various characteristics of the coating film.
[0186]
[Table 8]

[0187]
Examples 25-32, Comparative Examples 25-32:
A resin composition was obtained in the same manner as in the above embodiment except that the type of green pigment was variously changed.
[0188]
Table 9 shows the production conditions and various properties of the obtained resin composition.
[0189]
[Table 9]

[0190]
【The invention's effect】
The green pigment according to the present invention is suitable as a green pigment because it has high hiding power and coloring power, is excellent in heat resistance and weather resistance, and is harmless.
[0191]
The paint and resin composition according to the present invention are suitable as a green paint and resin composition in consideration of environmental pollution because they use green pigments that are excellent in heat resistance and chemical resistance and are harmless.

Claims (4)

The particle surface of the hydrous iron oxide powder is coated with an organosilane compound or polysiloxane generated from alkoxysilane, and an organic blue pigment is attached to the coating. Green color with an average major axis diameter of 0.1 to 1.0 μm It consists of composite hydrous iron oxide particle powder, and the coating amount of the organosilane compound or polysiloxane is 0.02 to 5.5 in terms of Si with respect to the organosilane compound coated hydrous iron oxide particle powder or polysiloxane coated hydrous iron oxide particle powder. The green pigment , characterized in that it is 0% by weight and the amount of the organic blue pigment adhered is 5 to 30 parts by weight with respect to 100 parts by weight of the hydrous iron oxide particle powder.  The particle surface of the hydrous iron oxide powder according to claim 1 is coated in advance with an intermediate coating composed of at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. A green pigment characterized by  A paint comprising the green pigment according to claim 1 or 2 blended in a paint-constituting substrate.  A resin composition characterized by being colored using the green pigment according to claim 1.