JP5177333B2 - Fine orange pigment, paint and resin composition using the fine orange pigment - Google Patents

Description

【００４３】
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。
【００４４】
有機赤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及び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より好ましい。
【００４５】
本発明におけるポリシロキサンは、化６で表わされるポリシロキサン、化７で表わされる変成ポリシロキサン、化８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。
【００４６】
【化６】

【００４７】
【化７】

【００４８】
【化８】

【００４９】
有機赤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。
【００５０】
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微粒子粉末、又は、ポリシロキサン被覆含水酸化鉄微粒子粉末に対して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。
【００５１】
０．０２重量％未満の場合には、含水酸化鉄微粒子粉末１００重量部に対して１重量部以上の有機赤色顔料を付着させることが困難である。
【００５２】
５．０重量％を超える場合には、含水酸化鉄微粒子粉末１００重量部に対して有機赤色顔料を１〜３０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。
【００５３】
本発明における有機赤色顔料は、キナクリドンレッド等のキナクリドン系顔料、パーマネントレッド等のアゾ系顔料、縮合アゾレッド等の縮合アゾ系顔料及びペリレンレッド等のペリレン系顔料を用いることができる。耐熱性及び耐光性を考慮した場合、キナクリドン系顔料を用いることが好ましい。
【００５４】
有機赤色顔料の付着量は、含水酸化鉄微粒子粉末１００重量部に対して１〜３０重量部である。
【００５５】
１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微細なオレンジ色系顔料を得ることが困難となる。より好ましくは３〜２５重量部である。
【００５６】
本発明に係る微細なオレンジ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微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。
【００５７】
即ち、本発明に係る微細なオレンジ色系顔料は、平均長軸径が０．００５μｍ以上で０．１μｍ未満、好ましくは０．００８〜０．０９６μｍ、より好ましくは０．０１〜０．０９２μｍである。
【００５８】
微細なオレンジ色系顔料の平均長軸径が０．１μｍ以上の場合には、粒子サイズが大きいため、隠蔽力が高くなり、該微細なオレンジ色系顔料を用いて得られた塗膜や樹脂組成物は、十分な透明性を有さない。平均長軸径が０．００５μｍ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。
【００５９】
本発明に係る微細なオレンジ色系顔料の形状は、針状又は直方体状である。
【００６０】
本発明に係る微細なオレンジ色系顔料の軸比は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。
【００６１】
本発明に係る微細なオレンジ色系顔料の平均短軸径は、０．００２５μｍ以上で０．０５μｍ未満が好ましく、より好ましくは０．００４〜０．０４８μｍであって、更に好ましくは０．００５〜０．０４６μｍである。０．００２５μｍ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おこしやすいため、ビヒクル中や樹脂組成物中への分散が困難となる。平均短軸径が０．０５μｍ以上のものは、工業的に得ることが困難である。
【００６２】
本発明に係る微細なオレンジ色系顔料の粒子径の幾何標準偏差値は、１．８以下であることが好ましい。１．８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１．７以下である。工業的な生産性を考慮すれば、微細なオレンジ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。
【００６３】
本発明に係る微細なオレンジ色系顔料のＢＥＴ比表面積値は５０〜３００ｍ^２／ｇが好ましく、より好ましくは７０〜２８０ｍ^２／ｇ、更により好ましくは８０〜２５０ｍ^２／ｇである。ＢＥＴ比表面積値が５０ｍ^２／ｇ未満の場合には、オレンジ色系顔料が粗大であるため、隠蔽力が高くなり、該微細なオレンジ色系顔料を用いて得れらた塗膜や樹脂組成物は、十分な透明性を有さない。ＢＥＴ比表面積値が３００ｍ^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。
【００６４】
本発明に係る微細なオレンジ色系顔料の有機赤色顔料の脱離率は１５％以下が好ましく、より好ましくは１２％以下である。有機赤色顔料の脱離率が１５％を超える場合には、脱離した有機赤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微粒子粉末の色相が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。
【００６５】
本発明に係る微細なオレンジ色系顔料の色相は、Ｌ^＊値が２５〜８０、ａ^＊値が＋１０〜＋１００、ｂ^＊値が＋３０〜＋１００及びｈ値が３０〜６０°の範囲のものである。
【００６６】
本発明に係る微細なオレンジ色系顔料の耐熱性は、芯粒子粉末である含水酸化鉄微粒子粉末の耐熱温度に対して＋５〜＋４０℃程度向上し、好ましくは２１０℃以上、より好ましくは２１５℃以上である。
【００６７】
本発明に係る微細なオレンジ色系顔料の着色力は、後述する評価方法で１１５％以上が好ましく、より好ましくは１２０％以上である。
【００６８】
本発明に係る微細なオレンジ色系顔料の隠蔽力は、６００ｃｍ^２／ｇ未満が好ましく、より好ましくは５００ｃｍ^２／ｇ以下である。隠蔽力が６００ｃｍ^２／ｇ以上の場合には、隠蔽力が高すぎるため、該微細なオレンジ色系顔料を用いて得られた塗膜や樹脂組成物は十分な透明性を有さない。
【００６９】
本発明に係る微細なオレンジ色系顔料の耐薬品性は、後述する評価方法で、耐酸性はΔＥ^＊値が１．５以下が好ましく、より好ましくは１．３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１．３以下である。
【００７０】
本発明に係る微細なオレンジ色系顔料は、必要により、含水酸化鉄微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種からなるの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、含水酸化鉄微粒子粉末の粒子表面からの有機赤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。
【００７１】
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微粒子粉末に対して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。
【００７２】
０．０１重量％未満である場合には、有機赤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、有機赤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。
【００７３】
中間被覆物で被覆されている本発明に係る微細なオレンジ色系顔料は、中間被覆物で被覆されていない本発明に係る微細なオレンジ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、微細なオレンジ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、耐熱処理を施していない芯粒子粉末を用いた微細なオレンジ色系顔料に対して＋５〜＋３０℃程度向上する。
【００７４】
次に、本発明に係る微細なオレンジ色系顔料を配合した塗料について述べる。
【００７５】
本発明に係る微細なオレンジ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１．３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２２０℃以上、好ましくは２２５℃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３０〜８５、ａ^＊値が＋１０〜＋１００、ｂ^＊値が＋３０〜＋１００及びｈ値が３０〜６０°であり、塗膜の透明性は線吸収係数が０．０５μｍ^−１以下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微細なオレンジ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１．３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２３０℃以上、好ましくは２３５℃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３０〜８５、ａ^＊値が＋１０〜＋１００、ｂ^＊値が＋３０〜＋１００及びｈ値が３０〜６０°であり、塗膜の透明性は線吸収係数が０．０５μｍ^−１以下であることが好ましい。
【００７７】
本発明に係る微細なオレンジ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１．３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２２０℃以上、好ましくは２２５℃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３０〜８５、ａ^＊値が＋１０〜＋１００、ｂ^＊値が＋３０〜＋１００及びｈ値が３０〜６０°であり、塗膜の透明性は線吸収係数が０．０５μｍ^−１以下であることが好ましい。
【００７８】
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微細なオレンジ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１．３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２３０℃以上、好ましくは２３５℃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３０〜８５、ａ^＊値が＋１０〜＋１００、ｂ^＊値が＋３０〜＋１００及びｈ値が３０〜６０°であり、塗膜の透明性は線吸収係数が０．０５μｍ^−１以下であることが好ましい。
【００７９】
本発明に係る塗料中における微細なオレンジ色系顔料の配合割合は、塗料構成基材１００重量部に対して０．５〜１００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１．０〜８０重量部、更に好ましくは１．０〜５０重量部である。
【００８０】
塗料構成基材としては、微細なオレンジ色系顔料、樹脂、溶剤と共に、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。
【００８１】
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。
【００８２】
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、シンナー、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、脂肪族炭化水素等及びこれらの混合物を用いることができる。
【００８３】
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。
【００８４】
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。
【００８５】
次に、本発明に係る微細なオレンジ色系顔料を用いて着色した樹脂組成物について述べる。
【００８６】
本発明に係る微細なオレンジ色系顔料を用いて着色した樹脂組成物の目視観察による分散状態は、後述評価法による４又は５、好ましくは５であり、樹脂組成物の耐熱温度は２１０℃以上、好ましくは２１５℃以上であって、色相はＬ^＊値が３０〜８５、ａ^＊値が＋１０〜＋１００、ｂ^＊値が＋３０〜＋１００及びｈ値が３０〜６０°であり、塗膜の透明性は線吸収係数が０．０５μｍ^−１以下であることが好ましい。
【００８７】
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微細なオレンジ色系顔料を用いて着色した樹脂組成物の目視観察による分散状態は、後述評価法による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３０〜８５、ａ^＊値が＋１０〜＋１００、ｂ^＊値が＋３０〜＋１００及びｈ値が３０〜６０°であり、塗膜の透明性は線吸収係数が０．０５μｍ^−１以下であることが好ましい。
【００８８】
本発明に係る樹脂組成物中における微細なオレンジ色系顔料の配合割合は、樹脂１００重量部に対して０．０１〜５０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０．０５〜４５重量部、更に好ましくは０．１〜４０重量部である。
【００８９】
本発明に係る樹脂組成物における構成基材としては、微細なオレンジ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。
【００９０】
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。
【００９１】
添加剤の量は、微細なオレンジ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。
【００９２】
本発明に係る樹脂組成物は、樹脂原料と微細なオレンジ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、微細なオレンジ色系顔料の凝集体を破壊し、樹脂組成物中に微細なオレンジ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。
【００９３】
次に、本発明に係る微細なオレンジ色系顔料の製造法について述べる。
【００９４】
本発明に係る微細なオレンジ色系顔料は、含水酸化鉄微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、含水酸化鉄微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微粒子粉末と有機赤色顔料を混合することによって得ることができる。
【００９５】
含水酸化鉄微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、含水酸化鉄微粒子粉末とアルコキシシラン又はポリシロキサンとを機械的に混合攪拌したり、含水酸化鉄微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微粒子粉末の粒子表面に被覆される。
【００９６】
なお、被覆されたアルコキシシランは、その１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赤色顔料の付着に影響することはない。
【００９７】
含水酸化鉄微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赤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含水酸化鉄微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。
【００９８】
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。
【００９９】
混合撹拌時における条件は、含水酸化鉄微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。
【０１００】
アルコキシシラン又はポリシロキサンの添加量は、含水酸化鉄微粒子粉末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、目的とする微細なオレンジ色系顔料を得られるだけの有機赤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、含水酸化鉄微粒子粉末１００重量部に対して有機赤色顔料を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。
【０１０１】
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微粒子粉末に有機赤色顔料を添加し、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赤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。
【０１０２】
有機赤色顔料は、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。
【０１０３】
混合攪拌時における条件は、有機赤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。
【０１０４】
有機赤色顔料の添加量は、含水酸化鉄微粒子粉末１００重量部に対して１〜３０重量部である。有機赤色顔料の添加量が上記範囲外の場合には、目的とする微細なオレンジ色系顔料が得られない。
【０１０５】
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。
【０１０６】
得られた微細なオレンジ色系顔料の被覆に用いられたアルコキシシランは、これらの工程を経ることにより、最終的には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なって被覆されている。
【０１０７】
含水酸化鉄微粒子粉末は、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。
【０１０８】
中間被覆物による被覆は、含水酸化鉄微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、前記含水酸化鉄微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。
【０１０９】
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。
【０１１０】
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。
【０１１１】
【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。
【０１１２】
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。
【０１１３】
軸比は、平均長軸径と平均短軸径との比で示した。
【０１１４】
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。
【０１１５】
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、粒子の長軸径の粒度分布が優れていることを意味する。
【０１１６】
比表面積値は、ＢＥＴ法により測定した値で示した。
【０１１７】
含水酸化鉄微粒子粉末及び含水酸化鉄微粒子粉末の粒子内部や粒子表面に存在しているＡｌ量、Ｓｉ量、含水酸化鉄微粒子粉末の粒子表面に被着されているアルミニウムと鉄からなる複合含水酸化物中に含有されているＡｌ量及び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。
【０１１８】
尚、含水酸化鉄微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。
【０１１９】
含水酸化鉄微粒子の粒子表面に被着させたアルミニウムと鉄からなる複合含水酸化物層中のＦｅ量は、下記の方法により、濾液中のＡｌ量及びＦｅ量から求めたＦｅに対するＡｌ量の重量比と前記蛍光Ｘ線分析より求めた複合含水酸化物層中のＡｌ重量％とから、数１に従って算出した値で示した。
【０１２０】
即ち、含水酸化鉄微粒子粉末０．２５ｇを１００ｍｌの三角フラスコに秤り取り、イオン交換水３３．３ｍｌを加え、６０℃に加温したウォータバス中で、マグネチックスターラーを用いて２０分間攪拌し、分散懸濁液とした。次いで、１２Ｎの塩酸を１６．７ｍｌ加え、更に２０分間攪拌して、含水酸化鉄微粒子の粒子表面に被着されているアルミニウムと鉄からなる複合含水酸化物の最外表面から粒子の内部方向に向けて、含水酸化鉄微粒子の表面までの距離の中央部位までの組成が実質的に均一である部分を酸溶解した（数多くの実験結果に基づいて確認している）。この酸溶解懸濁液を０．１μｍのメンブランフィルターを用いて吸引濾過を行い、得られた濾液中のＡｌ量（ｐｐｍ）及びＦｅ量（ｐｐｍ）のそれぞれを誘導プラズマ発光分光分析装置ＳＰＳ４０００（セイコー電子工業株式会社製）を用いて測定した。
【０１２１】
【数１】
Ｆｅ重量％＝Ａｌ重量％／Ｆｅに対するＡｌの重量比
【０１２２】
微細なオレンジ色系顔料に付着している有機赤色顔料の付着量は、「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。
【０１２３】
微細なオレンジ色系顔料に付着している有機赤色顔料の脱離率（％）は、下記の方法により求めた値で示した。有機赤色顔料の脱離率が０％に近いほど、微細なオレンジ色系顔料の粒子表面からの有機赤色顔料の脱離量が少ないことを示す。
【０１２４】
微細なオレンジ色系顔料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、沈降速度によって微細なオレンジ色系顔料と脱離した有機赤色顔料とを分離した。次いで、この微細なオレンジ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、微細なオレンジ色系顔料と脱離した有機赤色顔料を分離した。この微細なオレンジ色系顔料を８０℃で１時間乾燥させ、有機赤色顔料の量を測定し、下記数２に従って求めた値を有機赤色顔料の脱離率（％）とした。
【０１２５】
【数２】
有機赤色顔料の脱離率（％）＝{（Ｗａ−Ｗｅ）／Ｗａ}×１００
Ｗａ：微細なオレンジ色系顔料の有機赤色顔料付着量
Ｗｅ：脱離テスト後の微細なオレンジ色系顔料の有機赤色顔料付着量
【０１２６】
含水酸化鉄微粒子粉末、有機赤色顔料及び微細なオレンジ色系顔料の色相は、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−ｓｐｅｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いて、Ｌ^＊値、ａ^＊値及びｂ^＊値を測定した。
【０１２７】
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３に従って求めることができる。
【０１２８】
【数３】
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）
【０１２９】
含水酸化鉄微粒子粉末及び微細なオレンジ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。
【０１３０】
微細なオレンジ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−ｓｐｅｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いてＬ^＊値を測定し、その差をΔＬ^＊値とした。
【０１３１】
次いで、各微細なオレンジ色系顔料の標準試料として、各微細なオレンジ色系顔料と同様の割合で有機赤色顔料と含水酸化鉄粒子粉末とを単に混合した混合顔料を用いて、上記と同様にして原色エナメルと展色エナメルの塗布片を作製し、各塗布片のＬ^＊値を測色し、その差をΔＬｓ^＊値とした。
【０１３２】
得られた各微細なオレンジ色系顔料のΔＬ^＊値と標準試料のΔＬｓ^＊値を用いて下記数４に従って算出した値を着色力（％）として示した。
【０１３３】
【数４】
着色力（％）＝１００＋｛（ΔＬｓ^＊−ΔＬ^＊）×１０｝
【０１３４】
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。
【０１３５】
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。
【０１３６】
含水酸化鉄微粒子粉末及び微細なオレンジ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。
【０１３７】
含水酸化鉄微粒子粉末及び微細なオレンジ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膜を作製し、Ｌ^＊値、ａ^＊値及びｂ^＊値を測色し、下記数５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。
【０１３８】
含水酸化鉄微粒子粉末及び微細なオレンジ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膜を作製し、Ｌ^＊値、ａ^＊値及びｂ^＊値を測色し、下記式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。
【０１３９】
【数５】
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
【０１４０】
微細なオレンジ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、微細なオレンジ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。
【０１４１】
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。
【０１４２】
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、微細なオレンジ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。
【０１４３】
微細なオレンジ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透明性は、後述する処法によって調製した塗料を厚さ１００μｍのクリアベースフィルムに１５０μｍ（６ｍｉｌ）の厚さで塗布して得られた塗膜について、樹脂組成物の透明性は後述する組成から成る樹脂プレートについて、「自記光電分光光度計ＵＶ−２１００」（株式会社島津製作所製）を用いて測定した光透過率から、下記数６によって定義される線吸収係数で示した。線吸収係数は値が小さいほど光を透しやすく透明性が高いことを示す。
【０１４４】
【数６】
線吸収係数（μｍ^−１）＝ｌｎ（１／ｔ）／ＦＴ
ｔ：λ＝９００ｎｍにおける光透過率（−）
ＦＴ：測定に用いた塗膜の厚み又は樹脂プレートの厚み（μｍ）
【０１４５】
微細なオレンジ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耐熱性は、後述する処法によって調製した塗料を透明ガラス板（０．８ｍｍ（厚）×７０ｍｍ（幅）×１５０ｍｍ（長さ））に１５０μｍ（６ｍｉｌ）の厚さで塗布し、その塗布板を電気炉に入れ、電気炉の温度を種々変化させて各温度において１５分間熱処理を行い、塗布板の各温度における熱処理前後での色相（Ｌ^＊値、ａ^＊値、ｂ^＊値）を標準白色板をバックにして、多光源分光測色計（ＭＳＣ−ＩＳ−２Ｄ、スガ試験機株式会社製）Ｍｕｌｔｉ−ｓｐｅｃｔｒｏ−ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いてそれぞれ測定した。熱処理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塗膜の耐熱温度とした。
【０１４６】
樹脂組成物の耐熱性は後述する処法によって作製した樹脂プレートを５ｃｍ角に裁断し、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分間熱処理を行い、樹脂プレートの各温度における熱処理前後での色相（Ｌ^＊値、ａ^＊値、ｂ^＊値）の変化をそれぞれ測定し、熱処理前の測色値を基準に下記数７で示されるΔＥ^＊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。
【０１４７】
【数７】
ΔＥ^＊値＝（（ΔＬ^＊）^２＋（Δａ^＊）^２＋（Δｂ^＊）^２）^１／２
ΔＬ^＊値：塗膜又は樹脂プレートの熱処理前後のＬ^＊値の差
Δａ^＊値：塗膜又は樹脂プレートの熱処理前後のａ^＊値の差
Δｂ^＊値：塗膜又は樹脂プレートの熱処理前後のｂ^＊値の差
【０１４８】
塗料の貯蔵安定性は、後述する処法によって調製した塗料をクリアベースフィルムに１５０μｍ（６ｍｉｌ）の厚みで塗布、乾燥して製造した塗膜の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クリアベースフィルムに塗布、乾燥して製造した塗膜のＬ^＊値、ａ^＊値及びｂ^＊値を測定し、下記数８に従って得られたΔＥ^＊値で示した。
【０１４９】
【数８】
ΔＥ^＊値＝（（ΔＬ^＊）^２＋（Δａ^＊）^２＋（Δｂ^＊）^２）^１／２
ΔＬ^＊値： 比較する塗布膜の静置前後のＬ^＊値の差
Δａ^＊値： 比較する塗布膜の静置前後のａ^＊値の差
Δｂ^＊値： 比較する塗布膜の静置前後のｂ^＊値の差
【０１５０】
塗膜の耐酸性は、上記耐熱性の評価と同様の方法で塗布板を作製し、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、上記塗布板を糸でつるして約１２０ｍｍの深さまで浸漬し、２５℃で２４時間静置する。
【０１５１】
次に、塗布板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、塗布板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。
【０１５２】
塗膜の耐アルカリ性は、上記耐熱性の評価と同様の方法で塗布板を作製し、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、上記塗布板を糸でつるして約１２０ｍｍの深さまで浸漬し、２５℃で２４時間静置する。
【０１５３】
次に、塗布板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、塗布板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。
【０１５４】
塗料粘度については、後述する処法によって調製した塗料の２５℃における塗料粘度を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。
【０１５５】
微細なオレンジ色系顔料の樹脂組成物への分散性は、後述する処法によって作製して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。
【０１５６】
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。
【０１５７】
＜微細なオレンジ色系顔料の製造＞
ゲータイト微粒子粉末（粒子形状：針状、平均長軸径０．０７１０μｍ、平均短軸径０．００８１μｍ、軸比８．８、幾何標準偏差値１．３８、ＢＥＴ比表面積値１５９．８ｍ^２／ｇ、アルミニウムの含有量０．８３重量％、Ｌ^＊値５１．６、ａ^＊値３１．４、ｂ^＊値６１．７、ｈ値６３．０°、耐酸性１．９２、耐アルカリ性１．７５、隠蔽力１５２ｃｍ^２／ｇ、耐熱性２４５℃）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：ＧＥ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微粒子粉末に添加し、４４１Ｎ／ｃｍ（４５Ｋｇ／ｃｍ）の線荷重で３０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。
【０１５８】
次に、有機赤色顔料Ａ（種類：キナクリドンレッド、粒子形状：粒状、平均長軸径０．５８μｍ、隠蔽力４８０ｃｍ^２／ｇ、Ｌ^＊値３７．０、ａ^＊値５１．９、ｂ^＊値２０．６、ｈ値２１．６°、耐熱性４８８℃）１１００ｇ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４４１Ｎ／ｃｍ（４５Ｋｇ／ｃｍ）の線荷重で３０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赤色顔料Ａを付着させた後、乾燥機を用いて１０５℃で６０分間加熱処理を行い、微細なオレンジ色系顔料を得た。なお、このときの撹拌速度は２２ｒｐｍで行った。
【０１５９】
得られた微細なオレンジ色系顔料は、平均長軸径が０．０７２０μｍ、平均短軸径が０．００８４μｍ、軸比が８．６の針状粒子粉末であった。幾何標準偏差値は１．３８、ＢＥＴ比表面積値は１６２．１ｍ^２／ｇ、Ｌ^＊値は３５．２、ａ^＊値は４９．８、ｂ^＊値は４０．２、ｈ値は３８．９°、着色力は１２９％、隠蔽力は１６１ｃｍ^２／ｇであり、耐薬品性のうち、耐酸性はΔＥ^＊値で１．０９、耐アルカリ性はΔＥ^＊値で１．０４であり、耐熱性は２５４℃、有機赤色顔料の脱離率は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０．３０重量％であった。
【０１６０】
電子顕微鏡写真観察の結果、有機赤色顔料Ａがほとんど認められないことから、有機赤色顔料Ａ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。
【０１６１】
＜微細なオレンジ色系顔料を含む溶剤系塗料の製造＞
２５０ｍｌのガラスビンに前記微細なオレンジ色系顔料５ｇと塗料組成基材を下記割合で配合して３ｍｍφガラスビーズ１６０ｇとともにペイントシェーカーで１２０分間混合分散し、ミルベースを作製した。
微細なオレンジ色系顔料 ９．９ 重量部、
メラミン樹脂（スーパーペッカミン Ｊ−８２０−６０
：商品名：大日本インキ化学工業株式会社製） １９．８ 重量部、
アルキッド樹脂（ベッコゾール １３０７−６０ＥＬ
：商品名：大日本インキ化学工業株式会社製） ３９．６ 重量部、
キシレン ２９．７ 重量部、
ブタノール １．０ 重量部。
【０１６２】
得られた溶剤系塗料の塗料粘度は３，１１９ｃＰ、塗料の貯蔵安定性は、ΔＥ^＊値で０．９５であった。
【０１６３】
上記溶剤系塗料をクリアベースフィルムに１５０μｍ（６ｍｉｌ）の厚みで塗布、乾燥して得られた塗膜の光沢度は８２．２％、色相はＬ^＊値が３６．０、ａ^＊値が４９．５、ｂ^＊値が４０．６、ｈ値が３９．４°、線吸収係数は０．０２０２μｍ^−１であった。
【０１６４】
次いで、上記溶剤系塗料を透明ガラス板（０．８ｍｍ（厚）×７０ｍｍ（幅）×１５０ｍｍ（長さ））に１５０μｍ（６ｍｉｌ）の厚みで塗布して得られた塗膜の耐酸性はΔＧ値で８．５％、耐アルカリ性はΔＧ値で８．０％であった。
【０１６５】
次に、塗膜の耐熱温度を求めるため、上記溶剤系塗料を用いて同様にして塗布板を５枚用意し、それぞれ２１０℃、２３０℃、２５０℃、２７０℃及び２９０℃に加熱されたギヤオーブン中に入れ、１５分間熱処理した後に取り出し、塗布板の色相値を測定し、熱処理前の色相値を基準としてΔＥ^＊値を求め、熱処理温度とΔＥ^＊値との関係からΔＥ^＊値が１．５となる温度を求めたところ、２５９℃であった。
【０１６６】
＜微細なオレンジ色系顔料を含む水系塗料の製造＞
２５０ｍｌのガラスビンに前記微細なオレンジ色系顔料５ｇと塗料組成基材を下記割合で配合して３ｍｍφガラスビーズ１６０ｇとともにペイントシェーカーで１２０分間混合分散し、ミルベースを作製した。
微細なオレンジ色系顔料 １０．１ 重量部、
水溶性メラミン樹脂 ９．３ 重量部、
（商品名：Ｓ−６９５：大日本インキ化学工業株式会社製）
水溶性アルキッド樹脂 ４０．７ 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 ０．２ 重量部、
（商品名：ノプコ８０３４：サンノプコ株式会社製）
水 ２８．２ 重量部、
ブチルセロソルブ １１．５ 重量部。
【０１６７】
得られた水系塗料の塗料粘度は３，２０９ｃＰ、貯蔵安定性はΔＥ^＊値で０．９２であった。
【０１６８】
上記水系塗料をクリアベースフィルムに１５０μｍ（６ｍｉｌ）の厚みで塗布、乾燥して得られた塗膜の光沢度は７８．８％、色相はＬ^＊値が３６．１、ａ^＊値が４９．４、ｂ^＊値が４０．２、ｈ値が３９．１°、線吸収係数は０．０２１５μｍ^−１であった。
【０１６９】
次いで、上記水系塗料を透明ガラス板（０．８ｍｍ（厚）×７０ｍｍ（幅）×１５０ｍｍ（長さ））に１５０μｍ（６ｍｉｌ）の厚みで塗布して得られた塗膜の耐酸性はΔＧ値で８．７％、耐アルカリ性はΔＧ値で８．１％であった。
【０１７０】
次に、塗膜の耐熱温度を求めるため、上記水系塗料を用いて同様にして塗布板を５枚用意し、それぞれ２１０℃、２３０℃、２５０℃、２７０℃及び２９０℃に加熱されたギヤオーブン中に入れ、１５分間熱処理した後に取り出し、塗布板の色相値を測定し、熱処理前の色相値を基準としてΔＥ^＊値を求め、熱処理温度とΔＥ^＊値との関係からΔＥ^＊値が１．５となる温度を求めたところ、２５６℃であった。
【０１７１】
＜樹脂組成物の製造＞
上記微細なオレンジ色系顔料０．５ｇとポリ塩化ビニル樹脂粉末１０３ＥＰ８Ｄ（日本ゼオン株式会社製）４９．５ｇ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。
【０１７２】
得られた混合粉末にステアリン酸カルシウムを１．０ｇ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。
【０１７３】
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、９８ＭＰａ（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色相はＬ^＊値が３６．２、ａ^＊値が４９．９、ｂ^＊値が４０．６、ｈ値が３９．１°、分散状態は５、線吸収係数は０．０２１１μｍ^−１であった。
【０１７４】
次に、樹脂組成物の耐熱温度を求めるため、着色樹脂プレートを５ｃｍ角に裁断した試験片５枚を用意し、それぞれ１８５℃、２００℃、２１５℃、２３０℃及び２４５℃に加熱されたホットプレス中に入れ、９８ＭＰａ（１トン／ｃｍ^２）の荷重を掛けながら、１０分間熱処理した後に取り出して樹脂プレートの色相値を測定し、熱処理前の色相値を基準としてΔＥ^＊値を求め、熱処理温度とΔＥ^＊値との関係からΔＥ^＊値が１．５となる温度を求めたところ、２２９℃であった。
【０１７５】
【作用】
本発明において最も重要な点は、含水酸化鉄微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、該被覆に有機赤色顔料が付着している微細なオレンジ色系顔料は、耐薬品性及び着色力に優れ、且つ、耐熱性が向上した無害なオレンジ色系顔料であるという事実である。
【０１７６】
本発明においてオレンジ色を呈する顔料が得られる理由としては、黄色のフィルムに赤い透明フィルムを重ねるとオレンジ色を呈するのと同じ原理で、隠蔽力が弱い有機赤色顔料によって黄色を呈する含水酸化鉄微粒子粉末を被覆することによって、オレンジ色に見えるものと考えている。
【０１７７】
本発明に係る微細なオレンジ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微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赤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。
【０１７８】
本発明に係る微細なオレンジ色系顔料が着色力に優れている理由としては、無機顔料の中では着色力に優れる含水酸化鉄微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赤色顔料を強固に固定化して複合化できたことによって、着色力に優れた顔料とすることができたものと考えている。
【０１７９】
本発明に係る微細なオレンジ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微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、該被覆上に耐熱性に優れている有機赤色顔料を固定化することによって、微細なオレンジ色系顔料の耐熱性が向上したものと考えている。
【０１８０】
また、本発明に係る微細なオレンジ色系顔料は、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。
【０１８１】
【実施例】
次に、実施例及び比較例を示す。
【０１８２】
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微粒子粉末を用意した。
【０１８３】
【表１】

【０１８４】
芯粒子５：
芯粒子１の針状ゲータイト微粒子粉末２０ｋｇと水１５０ｌとを用いて、針状ゲータイト微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微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５．０ｍｏｌ／ｌのアルミン酸ナトリウム溶液５４４４ｍｌ（針状ゲータイト微粒子粉末に対してＡｌ換算で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微粒子粉末を得た。
【０１８５】
このときの製造条件を表２に、得られた表面処理済み針状ゲータイト微粒子粉末の諸特性を表３に示す。
【０１８６】
芯粒子６〜８：
芯粒子２〜４の各含水酸化鉄微粒子粉末を用い、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微粒子粉末を得た。
【０１８７】
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微粒子粉末の諸特性を表３に示す。
【０１８８】
【表２】

【０１８９】
【表３】

【０１９０】
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。
【０１９１】
有機赤色顔料Ａ及びＢ：
有機赤色顔料として表４に示す諸特性を有する有機赤色顔料を用意した。
【０１９２】
【表４】

【０１９３】
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、有機赤色顔料の付着工程における有機赤色顔料の種類、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微細なオレンジ色系顔料を得た。
【０１９４】
このときの製造条件を表５に、得られた微細なオレンジ色系顔料の諸特性を表６に示す。
【０１９５】
【表５】

【０１９６】
【表６】

【０１９７】
実施例９〜１６、比較例６〜１０：
微細なオレンジ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。
【０１９８】
得られた塗料の諸特性及び塗膜の諸特性を表７に示す。
【０１９９】
【表７】

【０２００】
実施例１７〜２４、比較例１１〜１５：
微細なオレンジ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。
【０２０１】
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。
【０２０２】
【表８】

【０２０３】
実施例２５〜３２、比較例１６〜２０：
微細なオレンジ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。
【０２０４】
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。
【０２０５】
【表９】

【０２０６】
【発明の効果】
本発明に係る微細なオレンジ色系顔料は、無害であって、耐薬品性及び耐熱性が向上し、しかも、該微細なオレンジ色系顔料を用いることによって、優れた透明性を有する塗料及び樹脂組成物を得ることができるので、樹脂、塗料及び印刷インキ等の着色顔料として好適である。
【０２０７】
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、無害である微細なオレンジ色系顔料を用いることから、環境汚染を配慮し、且つ、透明性に優れたオレンジ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 is a fine orange pigment having improved chemical resistance such as acid resistance and alkali resistance without containing harmful elements, and having improved heat resistance. By using a pigment, a fine orange pigment capable of obtaining a paint and a resin composition having excellent transparency is provided.
[0002]
[Prior art]
Currently, chrome vermilion, red yellow chrome, permanent orange, benzidine orange, and the like are used as orange pigments, and are widely used as colored pigments for resins, paints, printing inks, and the like.
[0003]
Chrome vermilion and red-yellow chrome lead are known to be very expensive, but are inferior in chemical resistance such as acid and alkali, weather resistance and heat resistance, and are expensive.
[0004]
In addition, orange-based inorganic pigments such as chrome vermilion and red lead yellow lead are toxic because they contain lead and chromium as their constituent elements, so they are hygienic, safe, and prevent environmental pollution. Therefore, there is a strong demand for alternative orange pigments.
[0005]
On the other hand, organic orange pigments such as permanent orange and benzidine orange are known to have a clear hue but poor weather resistance and poor hiding power.
[0006]
In addition, since the resin composition using a thermoplastic resin such as polyethylene, polypropylene, polyolefin, styrene polymer, polyamide, ABS or the like is usually molded at a high temperature of 200 ° C. or higher, the orange added as a colorant is added. The color pigment is required to have heat resistance.
[0007]
Therefore, there is a strong demand for harmless orange pigments that are excellent in chemical resistance and coloring power and are excellent in heat resistance.
[0008]
Among the orange pigments, those composed of particles having a particle diameter of less than 0.1 μm can exhibit a transparency because a coating film transparent to light in the visible light region can be obtained when the coating is formed. It has been known.
[0009]
This fine orange pigment with a particle diameter of less than 0.1 μm is a fine particle and has a large specific surface area. Therefore, the heat resistance generally tends to decrease, and from this point, the heat resistance of the pigment itself is strongly demanded. Has been.
[0010]
In addition, since it is a fine particle, the surface energy of the powder is high and it tends to agglomerate, so the dispersibility in the vehicle or the resin composition is inferior. If the particles agglomerate into coarse particles, the coating film or resin composition It becomes difficult to exhibit sufficient transparency when made into an object.
[0011]
Therefore, there is a strong demand to improve the dispersibility of the fine orange pigment in the vehicle and the resin composition.
[0012]
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, JP-A-11-181329, etc.) have been proposed.
[0013]
[Problems to be solved by the invention]
Fine orange pigments that are excellent in chemical resistance and improved in heat resistance without containing harmful elements are currently in most demand, but have not yet been obtained.
[0014]
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.
[0015]
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.
[0016]
In the method described in the above-mentioned JP-A-11-181329, an organopolysiloxane is dissolved in a cyclic silicone, and an organic pigment is added to the resulting solution for atomization. This is a method of impregnating and then volatilizing the cyclic silicone, and it is difficult to say that the adhesion strength of the organic pigment is sufficient.
[0017]
Therefore, it is a technical object of the present invention to provide a fine orange pigment that is harmless and excellent in chemical resistance such as acid resistance and alkali resistance and improved in heat resistance.
[0018]
[Means for solving the problems]
The technical problem can be achieved by the present invention as follows.
[0019]
That is, according to the present invention, the average major axis diameter of 0.005 μm in which the particle surface of the hydrous iron oxide fine particle powder is coated with an organosilane compound or polysiloxane formed from alkoxysilane and the organic red pigment is adhered to the coating. It is composed of fine composite hydrous iron oxide fine particle powder of less than 0.1 μm as described above, and the adhesion amount of the organic red pigment is 1 to 30 parts by weight with respect to 100 parts by weight of the hydrous iron oxide fine particle powder. It is a fine orange pigment (Invention 1).
[0020]
Further, in the present invention, the particle surface of the hydrous iron oxide fine particle powder of the present invention 1 is an intermediate composed of at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide in advance. It is a fine orange pigment characterized by being covered with a coating (Invention 2).
[0021]
Further, the present invention is a paint characterized in that the fine orange pigment of the present invention 1 or the present invention 2 is blended in a paint constituting base material.
[0022]
Further, the present invention is a resin composition characterized by being colored using the fine orange pigment of the present invention 1 or the present invention 2.
[0023]
The configuration of the present invention will be described in more detail as follows.
[0024]
First, the fine orange pigment according to the present invention will be described.
[0025]
In the fine orange pigment according to the present invention, the surface of the hydrous iron oxide fine particles, which are the core particles, is coated with an organosilane compound or polysiloxane generated from alkoxysilane, and the organic red pigment adheres to the coating. It consists of fine composite hydrous iron oxide fine particles having an average major axis diameter of 0.005 μm or more and less than 0.1 μm.
[0026]
The shape of the hydrous iron oxide fine 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.
[0027]
The hydrous iron oxide fine particle powder in the present invention is a goethite (α-FeOOH) particle powder and a lipidocrosite (γ-FeOOH) particle powder. In view of the heat resistance of the obtained orange pigment, a hydrous iron oxide fine particle powder obtained by subjecting a hydrous iron oxide fine particle to a heat treatment is preferable, and specifically, a hydrous iron oxide obtained by treating the surface of the hydrous iron oxide fine particle with an aluminum compound. Fine particle powder, hydrous iron oxide fine particle powder containing aluminum inside hydrous iron oxide fine particle, hydrous iron oxide fine particle powder having a composite hydrous oxide layer composed of aluminum and iron on the surface of hydrous iron oxide fine particle, and heat treatment thereof A complexed hydrous iron oxide fine particle powder is preferred.
[0028]
The aluminum content of the hydrous iron oxide fine particle powder obtained by treating the hydrous iron oxide fine particle surface with an aluminum compound is 0.1 to 20.0% by weight in terms of Al with respect to the hydrous iron oxide fine particle powder. The aluminum content of the hydrous iron oxide fine particle powder containing aluminum therein is 0.05 to 50% by weight in terms of Al with respect to the hydrous iron oxide fine particle powder. The aluminum content in the composite hydrous oxide layer deposited on the surface of the hydrous iron oxide fine particle powder having the composite hydrous oxide layer composed of aluminum and iron on the hydrous iron oxide microparticles surface is It is 0.1 to 10% by weight in terms of Al with respect to the powder, and the iron content is 0.1 to 30% by weight in terms of Fe with respect to the hydrous iron oxide fine particle powder.
[0029]
The average major axis diameter of the hydrous iron oxide fine particle powder in the present invention is 0.005 μm or more and less than 0.1 μm.
[0030]
When the average major axis diameter is less than 0.005 μm, aggregation is likely to occur due to an increase in intermolecular force due to finer particles, so that the surface of particles of hydrous iron oxide fine particles can be uniformly coated with alkoxysilane or polysiloxane. Processing and uniform adhesion treatment with organic red pigment become difficult. When the average major axis diameter is 0.1 μm or more, the resulting fine orange pigment is also not preferable because the particles are coarse and the hiding power is increased.
[0031]
Considering the uniform coating treatment with alkoxysilane or polysiloxane and the uniform adhesion treatment with organic red pigment on the particle surface of the hydrous iron oxide fine particle powder and the hiding power of the resulting fine orange pigment, the average major axis diameter Is preferably 0.008 to 0.096 μm, more preferably 0.01 to 0.092 μm.
[0032]
The hydrous iron oxide fine particle powder in the present invention preferably has an average minor axis diameter of 0.0025 μm or more and less than 0.05 μm, more preferably 0.004 to 0.048 μm, still more preferably 0.005 to 0.00. 046 μm. The axial ratio is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and the lower limit is 2. The BET specific surface area value is 50 to 300 m.²/ G is preferred, more preferably 70-280 m²/ G, more preferably 80 to 250 m²/ G. The geometric standard deviation value of the major axis diameter is preferably 1.8 or less, more preferably 1.7 or less, and the lower limit is 1.01.
[0033]
When the average minor axis diameter is less than 0.0025 μm, the surface of particles of the hydrous iron oxide fine particle powder is uniformly coated with alkoxysilane or polysiloxane and the organic red pigment due to the increase in intermolecular force due to finer particles This makes it difficult to perform uniform adhesion treatment. Those having an average minor axis diameter of 0.05 μm or more are difficult to obtain industrially.
[0034]
BET specific surface area value is 50m²If it is less than / g, the hydrous iron oxide powder is coarse or particles are sintered between the particles, and the resulting fine orange pigment is also concealed as coarse particles. Since power increases, it is not preferable. BET specific surface area value is 300m²/ G exceeding, it tends to cause aggregation due to an increase in intermolecular force due to finer particles, so uniform coating treatment with alkoxysilane or polysiloxane on the particle surface of the hydrous iron oxide fine particle powder and organic red pigment A uniform adhesion process becomes difficult.
[0035]
When the geometrical standard deviation value of the major axis diameter exceeds 1.80, the uniform dispersion is hindered by the existing coarse particles, so that the uniform surface by the alkoxysilane or polysiloxane on the particle surface of the hydrous iron oxide fine particle powder is uniform. The coating treatment and the uniform adhesion treatment with the organic red pigment become 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.
[0036]
When the axial ratio exceeds 20, entanglement between particles increases, and it is difficult to uniformly coat the surface of the hydrous iron oxide fine particle powder with alkoxysilane or polysiloxane and uniformly adhere with the organic red pigment. It becomes.
[0037]
The hue of the hydrous iron oxide fine particle powder in the present invention is L^*Value is 40-80, a^*Value is -30 to +35, b^*The value is in the range of +30 to +100 and the h value is in the range of 60 to 120 °. L^*Value, a^*Value, b^*When the value and h value are out of the above ranges, it is difficult to obtain a fine orange pigment that is the object of the present invention.
[0038]
The hiding power of the hydrous iron oxide fine particle powder in the present invention is 600 cm.²/ G is preferred, more preferably 500 cm²/ G or less. Concealment power is 600cm²In the case of / g or more, since the hiding power is too high, the fine orange pigment obtained by using this as the core particle is also not preferred because the hiding power is also high.
[0039]
The chemical resistance of the hydrous iron oxide fine particle powder in the present invention is an evaluation method described later, and the acid resistance is ΔE.^*The value is preferably 3.0 or less, more preferably 2.5 or less, and the alkali resistance is ΔE.^*The value is preferably 3.0 or less, more preferably 2.5 or less. Acid and alkali resistant ΔE^*When the value exceeds 3.0, it becomes difficult to obtain a fine orange pigment excellent in chemical resistance, which is the object of the present invention.
[0040]
The hydrous iron oxide fine particle 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 resulting fine orange pigment, a hydrous iron oxide fine particle powder obtained by subjecting a hydrous iron oxide fine particle to heat treatment is preferable, and a hydrous iron oxide fine particle powder obtained by treating an aluminum compound on the hydrous iron oxide fine particle surface. In this case, the heat-resistant temperature is about 240 ° C., and in the case of the hydrous iron oxide fine powder containing aluminum inside the hydrous iron oxide fine particles, it is about 245 ° C. In the case of hydrous iron oxide fine powder having a composite hydrous oxide layer made of iron, the temperature is about 250 ° C.
[0041]
The organosilane compound produced from the alkoxysilane in the present invention (hereinafter referred to as “organosilane compound”)5It is an organosilane compound produced | generated from the alkoxysilane represented by these.
[0042]
[Chemical formula 5]

[0043]
Specific examples of the alkoxysilane include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane. Examples include methoxysilane and decyltrimethoxysilane.
[0044]
In view of the adhesion effect and desorption rate of the organic red pigment, an organosilane compound formed from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, and phenyltriethoxysilane is preferable. An organosilane compound produced from methyltrimethoxysilane and phenyltriethoxysilane is more preferable.
[0045]
The polysiloxane in the present invention is6A polysiloxane represented by7A modified polysiloxane represented by8The terminal modified polysiloxane represented by these, or a mixture thereof can be used.
[0046]
[Chemical 6]

[0047]
[Chemical 7]

[0048]
[Chemical 8]

[0049]
Considering the adhesion effect and desorption rate of the organic red 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.
[0050]
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 fine particle powder or the polysiloxane-coated iron oxide hydrous fine particle powder. More preferably, it is 0.03-4.0 weight%, More preferably, it is 0.05-3.0 weight%.
[0051]
When the amount is less than 0.02% by weight, it is difficult to attach 1 part by weight or more of organic red pigment to 100 parts by weight of the hydrous iron oxide fine particle powder.
[0052]
When it exceeds 5.0% by weight, 1 to 30 parts by weight of the organic red pigment can be attached to 100 parts by weight of the hydrous iron oxide fine particle powder, so that it is meaningless to coat more than necessary.
[0053]
As the organic red pigment in the present invention, a quinacridone pigment such as quinacridone red, an azo pigment such as permanent red, a condensed azo pigment such as condensed azo red, and a perylene pigment such as perylene red can be used. In view of heat resistance and light resistance, it is preferable to use a quinacridone pigment.
[0054]
The adhesion amount of the organic red pigment is 1 to 30 parts by weight per 100 parts by weight of the hydrous iron oxide fine particle powder.
[0055]
When the amount is less than 1 part by weight or exceeds 30 parts by weight, it is difficult to obtain a fine orange pigment that is the object of the present invention. More preferably, it is 3 to 25 parts by weight.
[0056]
The particle shape and particle size of the fine orange pigment according to the present invention greatly depend on the particle shape and particle size of the hydrous iron oxide fine particles, which are core particles, and have a particle form similar to the core particles.
[0057]
That is, the fine orange pigment according to the present invention has an average major axis diameter of 0.005 μm or more and less than 0.1 μm, preferably 0.008 to 0.096 μm, more preferably 0.01 to 0.092 μm. is there.
[0058]
When the average major axis diameter of the fine orange pigment is 0.1 μm or more, since the particle size is large, the hiding power is increased, and the coating film or resin obtained using the fine orange pigment The composition does not have sufficient transparency. When the average major axis diameter is less than 0.005 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.
[0059]
The fine orange pigment according to the present invention has a needle shape or a rectangular parallelepiped shape.
[0060]
The axial ratio of the fine orange pigment according to the present invention is preferably 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.
[0061]
The average minor axis diameter of the fine orange pigment according to the present invention is preferably 0.0025 μm or more and less than 0.05 μm, more preferably 0.004 to 0.048 μm, still more preferably 0.005 to 0.046 μm. When the particle size is less than 0.0025 μm, aggregation is likely to occur due to an increase in intermolecular force due to particle miniaturization, which makes it difficult to disperse in a vehicle or a resin composition. Those having an average minor axis diameter of 0.05 μm or more are difficult to obtain industrially.
[0062]
The geometric standard deviation value of the particle size of the fine orange pigment according to the present invention is preferably 1.8 or less. When it exceeds 1.8, it is difficult to uniformly disperse it in the vehicle or the resin composition due to the existing coarse particles. Considering uniform dispersion in the vehicle and the resin composition, it is preferably 1.7 or less. Considering industrial productivity, the lower limit of the geometric standard deviation value of the particle size of the fine orange pigment is 1.01, and those less than 1.01 are difficult to obtain industrially.
[0063]
The BET specific surface area value of the fine orange pigment according to the present invention is 50 to 300 m.²/ G is preferred, more preferably 70-280 m²/ G, even more preferably 80-250 m²/ G. BET specific surface area value is 50m²If it is less than / g, the orange pigment is coarse, so the hiding power is high, and the coating film and resin composition obtained using the fine orange pigment have sufficient transparency. Does not have. BET specific surface area value is 300m²When 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.
[0064]
The desorption rate of the organic red pigment of the fine orange pigment according to the present invention is preferably 15% or less, more preferably 12% or less. When the removal rate of the organic red pigment exceeds 15%, the released organic red pigment may inhibit uniform dispersion in the vehicle or the resin composition, and the water content of the detached portion may be reduced. Since the hue of the iron oxide fine particle powder appears on the particle surface, it is difficult to obtain a uniform hue.
[0065]
The hue of the fine orange pigment according to the present invention is L^*Value is 25-80, a^*Value is +10 to +100, b^*The value is in the range of +30 to +100 and the h value is in the range of 30 to 60 °.
[0066]
The heat resistance of the fine orange pigment according to the present invention is improved by about +5 to + 40 ° C., preferably 210 ° C. or more, more preferably 215 ° C. with respect to the heat resistance temperature of the hydrous iron oxide fine particle powder as the core particle powder. That's it.
[0067]
The coloring power of the fine orange pigment according to the present invention is preferably 115% or more, more preferably 120% or more by an evaluation method described later.
[0068]
The hiding power of the fine orange pigment according to the present invention is 600 cm.²/ G is preferred, more preferably 500 cm²/ G or less. Concealment power is 600cm²In the case of / g or more, since the hiding power is too high, the coating film and the resin composition obtained using the fine orange pigment do not have sufficient transparency.
[0069]
The chemical resistance of the fine orange 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 1.3 or less, and the alkali resistance is ΔE.^*The value is preferably 1.5 or less, more preferably 1.3 or less.
[0070]
The fine orange pigment according to the present invention is selected in advance from the hydroxide of aluminum, the oxide of aluminum, the hydroxide of silicon and the oxide of silicon, if necessary, as the particle surface of the hydrous iron oxide fine particle powder. It may be coated with an intermediate coating comprising at least one kind, and can reduce the detachment of the organic red pigment from the particle surface of the hydrous iron oxide fine particle powder as compared with the case where it is not coated with the intermediate coating. In addition, the heat resistance is slightly improved.
[0071]
The coating amount by the intermediate coating is Al equivalent to the hydrous iron oxide fine 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.
[0072]
When the amount is less than 0.01% by weight, the effect of reducing the desorption rate of the organic red pigment cannot be obtained. Since the effect of reducing the organic red pigment removal rate 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.
[0073]
The fine orange pigment according to the present invention coated with an intermediate coating has a particle size and geometric standard almost the same as those of the fine orange pigment according to the present invention not coated with an intermediate coating. Deviation value, BET specific surface area value, hue (L^*Value, a^*Value, b^*Value, h value), coloring power, hiding power and chemical resistance. The desorption rate of the fine orange 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 fine orange pigment using the core particle powder which has not performed the heat processing.
[0074]
Next, a paint containing the fine orange pigment according to the present invention will be described.
[0075]
The paint blended with the fine orange pigment according to the present invention has a storage stability of ΔE.^*The value is preferably 1.5 or less, more preferably 1.3 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 220 ° C. or higher, preferably 225 ° 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 30-85, a^*Value is +10 to +100, b^*The value is +30 to +100 and the h value is 30 to 60 °, and the transparency of the coating film has a linear absorption coefficient of 0.05 μm.^-1The following is preferable.
[0076]
The paint blended with a fine orange pigment whose particle surface is coated with an intermediate coating according to the present invention has a storage stability of ΔE.^*The value is preferably 1.5 or less, more preferably 1.3 or less. When the coating film is used, the glossiness is 80 to 115%, preferably 85 to 115%, and the heat resistance temperature of the coating film is 230 ° C. or higher, preferably 235 ° 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 30-85, a^*Value is +10 to +100, b^*The value is +30 to +100 and the h value is 30 to 60 °, and the transparency of the coating film has a linear absorption coefficient of 0.05 μm.^-1The following is preferable.
[0077]
The water-based paint containing the fine orange pigment according to the present invention has a storage stability of ΔE.^*The value is preferably 1.5 or less, more preferably 1.3 or less. When the coating film is used, the glossiness is 70 to 110%, preferably 75 to 110%, the heat resistance temperature of the coating film is 220 ° C. or higher, preferably 225 ° 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 30-85, a^*Value is +10 to +100, b^*The value is +30 to +100 and the h value is 30 to 60 °, and the transparency of the coating film has a linear absorption coefficient of 0.05 μm.^-1The following is preferable.
[0078]
The water-based paint blended with a fine orange 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 1.3 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 230 ° C. or higher, preferably 235 ° 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 30-85, a^*Value is +10 to +100, b^*The value is +30 to +100 and the h value is 30 to 60 °, and the transparency of the coating film has a linear absorption coefficient of 0.05 μm.^-1The following is preferable.
[0079]
The blending ratio of the fine orange-based pigment in the paint according to the present invention can be used in the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint constituent base material, taking into account the handling of the paint. For example, it is preferably 1.0 to 80 parts by weight, and more preferably 1.0 to 50 parts by weight.
[0080]
As a paint constituent substrate, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent, and the like are blended together with a fine orange pigment, a resin, and a solvent as necessary.
[0081]
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.
[0082]
As the solvent, it is possible to use toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, aliphatic hydrocarbons and the like, which are usually used for solvent-based paints, and mixtures thereof. it can.
[0083]
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.
[0084]
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.
[0085]
Next, the resin composition colored using the fine orange pigment according to the present invention will be described.
[0086]
The dispersion state by visual observation of the resin composition colored using the fine orange pigment according to the present invention is 4 or 5, preferably 5, according to the evaluation method described later, and the heat resistance temperature of the resin composition is 210 ° C. or higher. , Preferably 215 ° C. or higher, and the hue is L^*Value is 30-85, a^*Value is +10 to +100, b^*The value is +30 to +100 and the h value is 30 to 60 °, and the transparency of the coating film has a linear absorption coefficient of 0.05 μm.^-1The following is preferable.
[0087]
The dispersion state by visual observation of the resin composition colored using a fine orange pigment in which the particle surface according to the present invention is coated with an intermediate coating is 4 or 5, preferably 5, according to the evaluation method described below. The heat resistant temperature of the resin composition is 215 ° C. or higher, preferably 220 ° C. or higher, and the hue is L^*Value is 30-85, a^*Value is +10 to +100, b^*The value is +30 to +100 and the h value is 30 to 60 °, and the transparency of the coating film has a linear absorption coefficient of 0.05 μm.^-1The following is preferable.
[0088]
The blending ratio of the fine orange pigment in the resin composition according to the present invention can be used in the range of 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin, and the handling of the resin composition is taken into consideration. In this case, the amount is preferably 0.05 to 45 parts by weight, more preferably 0.1 to 40 parts by weight.
[0089]
As a constituent substrate in the resin composition according to the present invention, a fine orange pigment and a well-known thermoplastic resin, if necessary, addition of a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, various stabilizers, etc. An agent is blended.
[0090]
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.
[0091]
The amount of the additive may be 50% by weight or less based on the sum of the fine orange pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.
[0092]
The resin composition according to the present invention is prepared by mixing well a resin raw material and a fine orange pigment in advance, and then applying a strong shearing action under heating using a kneader or an extruder to produce a fine orange After destroying the aggregate of the pigment and uniformly dispersing the fine orange pigment in the resin composition, it is molded into a shape suitable for the purpose and used.
[0093]
Next, a method for producing a fine orange pigment according to the present invention will be described.
[0094]
The fine orange pigment according to the present invention is a mixture of hydrous iron oxide fine particle powder and alkoxysilane or polysiloxane, and the surface of the hydrous iron oxide fine particle powder is coated with alkoxysilane or polysiloxane. It can be obtained by mixing the hydrous iron oxide fine particle powder coated with polysiloxane and the organic red pigment.
[0095]
Coating the surface of the hydrous iron oxide fine particle powder with an alkoxysilane or polysiloxane is performed by mechanically mixing and stirring the hydrous iron oxide fine particle powder and the alkoxysilane or polysiloxane, or by adding the alkoxysilane or polysiloxane to the hydrous iron oxide fine particle powder. What is necessary is just to mechanically mix and stir while spraying siloxane. Almost all of the added alkoxysilane or polysiloxane is coated on the particle surface of the hydrous iron oxide fine particle powder.
[0096]
In addition, the coated alkoxysilane may be coated as an organosilane compound generated from an alkoxysilane, a part of which is generated through a coating process. Even in this case, the subsequent adhesion of the organic red pigment is not affected.
[0097]
Mixing and stirring the hydrous iron oxide fine particle powder and the alkoxysilane or polysiloxane, and mixing and stirring the organic red pigment and the hydrous iron oxide fine particle powder coated with the organosilane compound or polysiloxane generated from the alkoxysilane on the particle surface. As an apparatus for performing this, an apparatus capable of applying a shearing force to the powder layer is preferable. In particular, an apparatus capable of simultaneously performing shearing, spatula and compression, such as a wheel-type kneader, a ball-type kneader, and a blade. A mold kneader or a roll kneader can be used. In carrying out the present invention, a wheel-type kneader can be used more effectively.
[0098]
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.
[0099]
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 fine particle 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.
[0100]
The amount of alkoxysilane or polysiloxane added is preferably 0.15 to 45 parts by weight per 100 parts by weight of the hydrous iron oxide fine powder. When the amount is less than 0.15 parts by weight, it is difficult to deposit an organic red pigment sufficient to obtain a desired fine orange pigment. The addition amount of 0.15 to 45 parts by weight allows 5 to 30 parts by weight of the organic red pigment to be attached to 100 parts by weight of the hydrous iron oxide fine particle powder. meaningless.
[0101]
Next, the organic red pigment is added to the hydrous iron oxide fine particle powder coated with alkoxysilane or polysiloxane, and mixed and stirred to adhere the organic red pigment to the alkoxysilane coating or polysiloxane coating. If necessary, drying or heat treatment may be further performed.
[0102]
The organic red pigment is preferably added little by little over a period of about 5 to 60 minutes.
[0103]
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 red 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.
[0104]
The addition amount of the organic red pigment is 1 to 30 parts by weight with respect to 100 parts by weight of the hydrous iron oxide fine particle powder. When the amount of organic red pigment added is outside the above range, the desired fine orange pigment cannot be obtained.
[0105]
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.
[0106]
The alkoxysilane used for coating the obtained fine orange pigment is finally coated with an organosilane compound generated from the alkoxysilane through these steps.
[0107]
The hydrous iron oxide fine particle powder is at least selected from an aluminum hydroxide, an aluminum oxide, a silicon hydroxide, and a silicon oxide in advance of mixing and stirring with an alkoxysilane or polysiloxane if necessary. You may coat | cover with the intermediate coating which consists of 1 type.
[0108]
Coating with an intermediate coating is performed by adding an aluminum compound, a silicon compound, or both of the compounds to an aqueous suspension obtained by dispersing the hydrous iron oxide fine particle powder, and mixing and stirring, or if necessary, mixing and stirring. An intermediate coating comprising at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide on the particle surface of the hydrous iron oxide fine particle powder by adjusting the pH value later And then filter, wash, dry and grind. If necessary, a deaeration / consolidation process may be further performed.
[0109]
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.
[0110]
As the silicon compound, No. 3 water glass, sodium orthosilicate, sodium metasilicate and the like can be used.
[0111]
DETAILED DESCRIPTION OF THE INVENTION
A typical embodiment of the present invention is as follows.
[0112]
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.
[0113]
The axial ratio is shown as the ratio of the average major axis diameter to the average minor axis diameter.
[0114]
The particle size distribution of the major axis diameter of the particles is shown by the value obtained by the following method.
[0115]
That is, the value obtained by measuring the major axis diameter of the particle shown in the above enlarged photograph is calculated from the measured major axis diameter and the number of particles on the log normal probability paper according to a statistical method. The horizontal axis is plotted with the major axis diameter, and the vertical axis is plotted with the cumulative number of particles belonging to each of the predetermined major axis diameter sections (under integrated sieve) as a percentage. 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 major axis diameter of the particles.
[0116]
The specific surface area value was indicated by a value measured by the BET method.
[0117]
Hydrous iron oxide fine particle powder and hydrous iron oxide fine particle powder Al and Si present in the particle surface and particle surface, composite hydrous oxide composed of aluminum and iron deposited on the hydrous iron oxide fine particle powder surface Each of the amount of Al contained in the product and the amount of Si contained in the organosilane compound or polysiloxane uses a “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Corporation) and is JIS K0119. In accordance with “General X-ray fluorescence analysis rules”.
[0118]
In addition, each Si amount of silicon contained in the oxide of silicon, the hydroxide of silicon, and the organosilane compound covering the particle surface of the hydrous iron oxide fine particle powder or Si contained in the polysiloxane is a treatment step. The amount of Si was measured at each subsequent stage, and the value obtained by subtracting the amount of Si measured at the stage before the treatment process from the measured value was shown.
[0119]
The amount of Fe in the composite hydrous oxide layer composed of aluminum and iron deposited on the surface of the hydrous iron oxide fine particles was determined by the following method, and the weight of the Al amount relative to Fe obtained from the Al amount and the Fe amount in the filtrate. The value calculated according to Equation 1 from the ratio and the Al weight percent in the composite hydrous oxide layer determined from the fluorescent X-ray analysis.
[0120]
That is, 0.25 g of hydrous iron oxide fine particle powder was weighed into a 100 ml Erlenmeyer flask, added with 33.3 ml of ion-exchanged water, and stirred for 20 minutes using a magnetic stirrer in a water bath heated to 60 ° C. A dispersion suspension was obtained. Next, 16.7 ml of 12N hydrochloric acid was added, and the mixture was further stirred for 20 minutes. From the outermost surface of the composite hydrous oxide composed of aluminum and iron deposited on the surface of the hydrous iron oxide fine particles to the inside of the particles. For this purpose, a portion where the composition up to the central portion of the distance to the surface of the hydrous iron oxide fine particles was substantially uniform was dissolved in an acid (confirmed based on many experimental results). The acid-dissolved suspension was subjected to suction filtration using a 0.1 μm membrane filter, and each of the Al amount (ppm) and Fe amount (ppm) in the obtained filtrate was determined using an induction plasma emission spectroscopic analyzer SPS4000 (Seiko). Measured using an electronic industry).
[0121]
[Expression 1]
Fe weight% = Al weight% / weight ratio of Al to Fe
[0122]
The amount of organic red pigment adhering to the fine orange pigment is determined by measuring the amount of carbon using “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200” (manufactured by Horiba, Ltd.). It was.
[0123]
The desorption rate (%) of the organic red pigment adhering to the fine orange pigment was represented by the value obtained by the following method. The closer the organic red pigment detachment rate is to 0%, the smaller the organic red pigment detachment amount from the surface of fine orange pigment particles.
[0124]
Place 3 g of fine orange pigment and 40 ml of ethanol in a 50 ml settling tube, disperse ultrasonically for 20 minutes, leave it for 120 minutes, and then remove the organic red pigment separated from the fine orange pigment by the sedimentation speed. And separated. Next, 40 ml of ethanol was again added to the fine orange pigment, and after further ultrasonic dispersion for 20 minutes, the mixture was allowed to stand for 120 minutes to separate the fine orange pigment and the detached organic red pigment. This fine orange pigment was dried at 80 ° C. for 1 hour, the amount of the organic red pigment was measured, and the value determined according to the following formula 2 was taken as the desorption rate (%) of the organic red pigment.
[0125]
[Expression 2]
Desorption rate of organic red pigment (%) = {(Wa-We) / Wa} × 100
Wa: Organic red pigment adhesion amount of fine orange pigment
We: Organic orange pigment adhesion of fine orange pigment after desorption test
[0126]
The hues of the hydrous iron oxide fine powder, organic red pigment, and fine orange pigment were prepared by mixing 0.5 g of the sample and 0.5 ml of castor oil with a Hoover-type Mahler to form a paste. , Kneaded and converted into a paint, and applied to a cast-coated paper using a 150 μm (6 mil) applicator (coating thickness: about 30 μm). A multi-light source spectrocolorimeter (MSC) was applied to the coated piece. -IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Using Multi-spectro-color-Meter, L^*Value, a^*Value and b^*The value was measured.
[0127]
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 equation 3.
[0128]
[Equation 3]
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)
[0129]
The heat resistance of the hydrous iron oxide fine particle powder and the fine orange pigment was obtained by performing differential scanning calorimetry (DSC) of the measured particle powder using a thermal analyzer SSC5000 (manufactured by Seiko Denshi Kogyo Co., Ltd.). Of the two inflection points forming the peak shown on the DSC chart, a tangent line is drawn for each of the two curves constituting the first inflection point, and the temperature corresponding to the intersection of the two tangent lines is read. Indicated by temperature.
[0130]
The coloring power of the fine orange pigment is prepared by applying each of the primary color enamel and the color-enamel enamel produced according to the method shown below onto a cast-coated paper using a 150 μm (6 mil) applicator, About this application | coating piece, it is L using multi-spectro-color-meter for multi-light source spectrocolorimeter (MSC-IS-2D, Suga Test Instruments Co., Ltd. make).^*Measure the value and calculate the difference^*Value.
[0131]
Next, as a standard sample of each fine orange pigment, a mixed pigment obtained by simply mixing an organic red pigment and a hydrous iron oxide particle powder at the same ratio as each fine orange pigment is used as described above. Then, the coated pieces of primary color enamel and extended color enamel are prepared.^*Measure the value and calculate the difference ΔLs^*Value.
[0132]
ΔL of each fine orange pigment obtained^*Value and ΔLs of standard sample^*The value calculated according to the following formula 4 using the value was shown as coloring power (%).
[0133]
[Expression 4]
Coloring power (%) = 100 + {(ΔLs^*-ΔL^*) × 10}
[0134]
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.
[0135]
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.
[0136]
The hiding power of the hydrous iron oxide fine powder and the fine orange pigment was shown by the value obtained according to the cryptometer method of JIS K 5101 8.2 using the primary color enamel obtained above.
[0137]
The acid resistance of the hydrous iron oxide fine particle powder and the fine orange 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 it. A coating film was prepared in the same manner, and L^*Value, a^*Value and b^*The color difference ΔE measured according to the following formula 5^*Indicated by value. ΔE^*It shows that it is excellent in acid resistance, so that a value is small.
[0138]
The alkali resistance of the hydrous iron oxide fine powder and the fine orange pigment is determined by immersing 10 g of the sample powder in a 1% aqueous solution of caustic soda for 15 minutes, then removing the sample from the aqueous caustic soda 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 formula^*Indicated by value. ΔE^*It shows that it is excellent in alkali resistance, so that a value is small.
[0139]
[Equation 5]
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
[0140]
The hue of each coating film of the solvent-based paint and water-based paint obtained using the fine orange pigment is the cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS) The hue of the resin composition colored with a fine orange pigment using a coating piece for measurement obtained by coating and drying to form a coating film on G-3141) at a thickness of 150 μm is described later. Using the colored resin plate produced by the processing method, the multi-spctro-color-Meter multi-light source spectrocolorimeter (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) L^*Value, a^*Value and b^*The value was measured.
[0141]
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.
[0142]
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.). The higher the glossiness, the better the dispersibility of the paint containing a fine orange pigment.
[0143]
The transparency of each coating film of the solvent-based paint and the water-based paint obtained by using a fine orange pigment is determined by applying a paint prepared by the processing method described later to a clear base film having a thickness of 150 μm (6 mil). With respect to the coating film obtained by coating, the transparency of the resin composition was measured using a “self-recording photoelectric spectrophotometer UV-2100” (manufactured by Shimadzu Corporation) for a resin plate having the composition described below. From the light transmittance, it was shown by the linear absorption coefficient defined by the following formula 6. The smaller the value of the linear absorption coefficient, the easier it is to transmit light and the higher the transparency.
[0144]
[Formula 6]
Linear absorption coefficient (μm^-1) = Ln (1 / t) / FT
t: Light transmittance at λ = 900 nm (−)
FT: The thickness of the coating film used for the measurement or the thickness of the resin plate (μm)
[0145]
The heat resistance of each coating film of the solvent-based paint and water-based paint obtained by using a fine orange pigment was determined by applying a paint prepared by the method described later to a transparent glass plate (0.8 mm (thickness) x 70 mm (width) ) × 150 mm (length)) with a thickness of 150 μm (6 mils), and the coated plate is placed in an electric furnace, and the temperature of the electric furnace is variously changed and heat-treated at each temperature for 15 minutes. Hue before and after heat treatment at each temperature (L^*Value, a^*Value, b^*The value was measured using a multi-spectro-color-meter with a multi-light source spectrocolorimeter (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) with a standard white plate as the back. ΔE shown by the following equation 7 based on the colorimetric value before heat treatment^*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.
[0146]
The heat resistance of the resin composition was determined by cutting a resin plate produced by a method described later into 5 cm squares, subjecting it to hot pressing, and variously changing the hot pressing temperature to 98 MPa (1 ton / cm at each temperature).²) Is applied for 10 minutes while applying the load, and the hue (L^*Value, a^*Value, b^*Value), and ΔE expressed by the following equation 7 based on the colorimetric value before heat treatment.^*Using a semilogarithmic 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.
[0147]
[Expression 7]
ΔE^*Value = ((ΔL^*)²+ (Δa^*)²+ (Δb^*)²)^1/2
ΔL^*Value: L before and after heat treatment of paint film or resin plate^*Difference in values
Δa^*Value: a before and after heat treatment of coating film or resin plate^*Difference in values
Δb^*Value: b before and after heat treatment of coating film or resin plate^*Difference in values
[0148]
The storage stability of the paint is determined by applying the paint prepared by the processing method described later to a clear base film with a thickness of 150 μm (6 mil) and drying it.^*Value, a^*Value and b^*Value and the L of the coating film produced by applying the paint obtained by allowing it to stand at 25 ° C. for 1 week to the clear base film and drying it.^*Value, a^*Value and b^*The value was measured and ΔE obtained according to the following equation 8^*Indicated by value.
[0149]
[Equation 8]
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 leaving the coated film to be compared^*Difference in values
[0150]
For the acid resistance of the coating film, a coated plate is prepared by the same method as in the evaluation of the heat resistance, and the glossiness is measured. Next, a 5% by weight sulfuric acid aqueous solution is put into a 1000 ml beaker, the above-mentioned coated plate is hung with a thread, immersed to a depth of about 120 mm, and allowed to stand at 25 ° C. for 24 hours.
[0151]
Next, the coated plate is taken out of the sulfuric acid aqueous solution, gently washed with running water, shaken off the water, and the glossiness of the central portion of the coated plate 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.
[0152]
For the alkali resistance of the coating film, a coated plate is prepared by the same method as in the evaluation of the heat resistance, and the glossiness is measured. Next, a 1% aqueous solution of sodium hydroxide is put into a 1000 ml beaker, the coated plate is hung with a thread, dipped to a depth of about 120 mm, and allowed to stand at 25 ° C. for 24 hours.
[0153]
Next, the coated plate is taken out of the aqueous caustic soda solution, gently washed with running water, shaken off the water, and the glossiness of the central portion of the coated plate 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.
[0154]
Regarding the paint viscosity, the paint viscosity at 25 ° C. of the paint prepared by the method described later 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.
[0155]
The dispersibility of the fine orange pigment in the resin composition was evaluated on a five-point scale by visually determining the number of undispersed aggregated particles on the surface of the colored resin plate obtained by the method described later. . 5 indicates the best dispersion state.
[0156]
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.
[0157]
<Manufacture of fine orange pigments>
Goethite fine particle powder (particle shape: needle shape, average major axis diameter 0.0710 μm, average minor axis diameter 0.0081 μm, axial ratio 8.8, geometric standard deviation value 1.38, BET specific surface area value 159.8 m²/ G, aluminum content 0.83% by weight, L^*Value 51.6, a^*Value 31.4, b^*Value 61.7, h value 63.0 °, acid resistance 1.92, alkali resistance 1.75, hiding power 152 cm²/ G, heat resistance 245 ° C.) 11.0 kg was introduced into the edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Foundry Co., Ltd.) and methyltriethoxysilane (trade name: TSL8123: GE Toshiba Silicone Co., Ltd.) (Made by company) Methyltriethoxysilane solution obtained by mixing and diluting 220 g with 200 ml of ethanol was added to the above goethite fine particle powder while operating an edge runner, and a linear load of 441 N / cm (45 Kg / cm) for 30 minutes. Mixing and stirring were performed. The stirring speed at this time was 22 rpm.
[0158]
Next, organic red pigment A (kind: quinacridone red, particle shape: granular, average major axis diameter 0.58 μm, hiding power 480 cm²/ G, L^*Value 37.0, a^*Value 51.9, b^*(10.6 g of value 20.6, h value 21.6 °, heat resistance 488 ° C.) was added over 10 minutes while running the edge runner, and further mixed for 30 minutes with a linear load of 441 N / cm (45 Kg / cm). Stirring was performed to deposit the organic red pigment A on the methyltriethoxysilane coating, followed by heat treatment at 105 ° C. for 60 minutes using a dryer to obtain a fine orange pigment. The stirring speed at this time was 22 rpm.
[0159]
The resulting fine orange pigment was an acicular particle powder having an average major axis diameter of 0.0720 μm, an average minor axis diameter of 0.0084 μm, and an axial ratio of 8.6. Geometric standard deviation value is 1.38, BET specific surface area value is 162.1m²/ G, L^*The value is 35.2, a^*The value is 49.8, b^*Value is 40.2, h value is 38.9 °, coloring power is 129%, hiding power is 161 cm²/ G, out of chemical resistance, acid resistance is ΔE^*The value is 1.09 and the alkali resistance is ΔE^*The value is 1.04, the heat resistance is 254 ° C., the desorption rate of the organic red pigment is 7.0%, and the coating amount of the organosilane compound formed from methyltriethoxysilane is 0.30 weight in terms of Si. %Met.
[0160]
As a result of observing an electron micrograph, almost no organic red pigment A was observed. Thus, it was confirmed that almost all of the organic red pigment A was adhered to the organosilane compound coating formed from methyltriethoxysilane.
[0161]
<Manufacture of solvent-based paints containing fine orange pigments>
In a 250 ml glass bottle, 5 g of the fine orange pigment and a coating composition base material were blended in the following proportions and mixed and dispersed with a 3 mmφ glass bead 160 g with a paint shaker for 120 minutes to prepare a mill base.
9.9 parts by weight of a fine orange pigment,
Melamine resin (Super Peccamin J-820-60
: Product name: Dainippon Ink & Chemicals, Inc.) 19.8 parts by weight,
Alkyd resin (Beccosol 1307-60EL
: Product name: Dainippon Ink & Chemicals, Inc.) 39.6 parts by weight,
29.7 parts by weight of xylene,
Butanol 1.0 part by weight.
[0162]
The obtained solvent-based paint has a paint viscosity of 3,119 cP and the storage stability of the paint is ΔE.^*The value was 0.95.
[0163]
The above-mentioned solvent-based paint is applied to a clear base film with a thickness of 150 μm (6 mils) and dried.^*The value is 36.0, a^*The value is 49.5, b^*The value is 40.6, the h value is 39.4 °, and the linear absorption coefficient is 0.0202 μm.^-1Met.
[0164]
Next, the acid resistance of the coating film obtained by applying the solvent-based paint on a transparent glass plate (0.8 mm (thickness) x 70 mm (width) x 150 mm (length)) at a thickness of 150 μm (6 mil) is ΔG The value was 8.5%, and the alkali resistance was a ΔG value of 8.0%.
[0165]
Next, in order to determine the heat resistant temperature of the coating film, five coating plates were prepared in the same manner using the solvent-based paint, and the gears heated to 210 ° C, 230 ° C, 250 ° C, 270 ° C, and 290 ° C, respectively. Put in an oven, heat-treat for 15 minutes, take out, measure the hue value of the coated plate, ΔE based on the hue value before heat treatment^*Value, heat treatment temperature and ΔE^*ΔE from the relationship with the value^*The temperature at which the value was 1.5 was determined and found to be 259 ° C.
[0166]
<Manufacture of water-based paints containing fine orange pigments>
In a 250 ml glass bottle, 5 g of the fine orange pigment and a coating composition base material were blended in the following proportions and mixed and dispersed with a 3 mmφ glass bead 160 g with a paint shaker for 120 minutes to prepare a mill base.
Fine orange pigment 10.1 parts by weight,
9.3 parts by weight of water-soluble melamine resin,
(Product name: S-695: manufactured by Dainippon Ink & Chemicals, Inc.)
40.7 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
0.2 parts by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
28.2 parts by weight of water,
Butyl cellosolve 11.5 parts by weight.
[0167]
The resulting water-based paint has a paint viscosity of 3,209 cP and a storage stability of ΔE.^*The value was 0.92.
[0168]
The gloss obtained by applying the above water-based paint to a clear base film with a thickness of 150 μm (6 mil) and drying is 78.8%, and the hue is L^*The value is 36.1, a^*The value is 49.4, b^*The value is 40.2, the h value is 39.1 °, and the linear absorption coefficient is 0.0215 μm.^-1Met.
[0169]
Next, the acid resistance of the coating film obtained by applying the above water-based paint to a transparent glass plate (0.8 mm (thickness) × 70 mm (width) × 150 mm (length)) at a thickness of 150 μm (6 mil) is ΔG value. The alkali resistance was 8.1% in terms of ΔG value.
[0170]
Next, in order to determine the heat resistant temperature of the coating film, five coating plates were prepared in the same manner using the above water-based paint, and heated at 210 ° C, 230 ° C, 250 ° C, 270 ° C and 290 ° C, respectively. Put in, take out after heat treatment for 15 minutes, measure the hue value of the coated plate, ΔE based on the hue value before heat treatment^*Value, heat treatment temperature and ΔE^*ΔE from the relationship with the value^*The temperature at which the value was 1.5 was determined and found to be 256 ° C.
[0171]
<Manufacture of resin composition>
The fine orange pigment 0.5 g and polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.) 49.5 g are weighed, put in a 100 ml poly beaker and mixed well with a spatula to obtain a mixed powder. It was.
[0172]
After adding 1.0 g of calcium stearate to the obtained mixed powder and mixing, and setting the clearance of the 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.
[0173]
Next, the resin composition is sandwiched between surface-polished stainless steel plates and placed in a hot press heated to 180 ° C. and 98 MPa (1 ton / cm²) To obtain a colored resin plate having a thickness of 1 mm. The hue of the obtained colored resin plate is L^*The value is 36.2, a^*The value is 49.9, b^*Value is 40.6, h value is 39.1 °, dispersion state is 5, linear absorption coefficient is 0.0211 μm^-1Met.
[0174]
Next, in order to obtain the heat resistant temperature of the resin composition, five test pieces obtained by cutting the colored resin plate into 5 cm squares were prepared and heated to 185 ° C., 200 ° C., 215 ° C., 230 ° C. and 245 ° C., respectively. 98 MPa (1 ton / cm²), The resin plate is taken out and measured for hue value, and ΔE is measured based on the hue value before heat treatment.^*Value, heat treatment temperature and ΔE^*ΔE from the relationship with the value^*The temperature at which the value was 1.5 was determined and found to be 229 ° C.
[0175]
[Action]
In the present invention, the most important point is that the surface of the particles of the hydrous iron oxide fine particle powder is coated with an organosilane compound or polysiloxane generated from alkoxysilane, and a fine orange having an organic red pigment attached to the coating. The color pigment is a fact that it is a harmless orange pigment having excellent chemical resistance and coloring power and improved heat resistance.
[0176]
The reason why an orange-colored pigment can be obtained in the present invention is that the hydrous iron oxide fine particles exhibiting a yellow color due to an organic red pigment having a low hiding power on the same principle as when a red transparent film is superimposed on a yellow film. By coating the powder, it appears to look orange.
[0177]
The reason why the fine orange pigment according to the present invention is excellent in chemical resistance is that the iron oxide hydroxide fine particle powder as the core particle powder is excellent in chemical resistance and the organic red color adhered to the particle powder. It is considered that the chemical resistance of the whole particle is further improved by selecting a pigment having excellent chemical resistance.
[0178]
The reason why the fine orange pigment according to the present invention is excellent in coloring power is as follows. It is considered that a pigment having excellent coloring power can be obtained by firmly immobilizing the red pigment.
[0179]
The reason why the heat resistance of the fine orange pigment according to the present invention is excellent is that the hydrous iron oxide fine powder powder originally inferior in heat resistance is coated with an organosilane compound or polysiloxane excellent in heat resistance, and It is considered that the heat resistance of the fine orange pigment is improved by immobilizing an organic red pigment having excellent heat resistance on the coating.
[0180]
In addition, the fine orange 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.
[0181]
【Example】
Next, examples and comparative examples are shown.
[0182]
Core particles 1 to 4:
As the core particle powder, a hydrous iron oxide fine particle powder having the characteristics shown in Table 1 was prepared.
[0183]
[Table 1]

[0184]
Core particle 5:
Using 20 kg of acicular goethite fine particle powder of core particle 1 and 150 l of water, a slurry containing acicular goethite fine particle powder was obtained. The pH value of the redispersed slurry containing the obtained acicular goethite fine particle powder was adjusted to 10.5 using an aqueous sodium hydroxide solution, and 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 5444 ml of a 5.0 mol / l sodium aluminate solution (corresponding to 5% by weight in terms of Al with respect to acicular goethite fine particle powder) was added to this slurry, and 30 minutes After holding, 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 were performed to obtain acicular goethite fine particle powder whose particle surface was coated with aluminum hydroxide.
[0185]
The production conditions at this time are shown in Table 2, and various characteristics of the obtained surface-treated acicular goethite fine particle powder are shown in Table 3.
[0186]
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 fine particle powder of core particles 2 to 4 is used and the type and amount of the surface coating are variously changed. An iron fine particle powder was obtained.
[0187]
The production conditions at this time are shown in Table 2, and the properties of the obtained surface-treated hydrous iron oxide fine particle powder are shown in Table 3.
[0188]
[Table 2]

[0189]
[Table 3]

[0190]
In the surface treatment step, the type of coating A is an aluminum hydroxide, and S represents a silicon oxide.
[0191]
Organic red pigments A and B:
An organic red pigment having various characteristics shown in Table 4 was prepared as an organic red pigment.
[0192]
[Table 4]

[0193]
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 of edge runner treatment, types of organic red pigment in the process of attaching organic red pigment, amounts added, and lines of edge runner treatment A fine orange pigment was obtained in the same manner as in the above embodiment except that the load and time were variously changed.
[0194]
The production conditions at this time are shown in Table 5, and various characteristics of the obtained fine orange pigment are shown in Table 6.
[0195]
[Table 5]

[0196]
[Table 6]

[0197]
Examples 9-16, Comparative Examples 6-10:
A paint was obtained in the same manner as in the above embodiment except that the kind of the fine orange pigment was variously changed.
[0198]
Table 7 shows various properties of the obtained paint and various properties of the coating film.
[0199]
[Table 7]

[0200]
Examples 17-24, Comparative Examples 11-15:
A water-based paint was obtained in the same manner as in the above-described embodiment except that the type of the fine orange-based pigment was variously changed.
[0201]
Table 8 shows various characteristics of the obtained water-based paint and various characteristics of the coating film.
[0202]
[Table 8]

[0203]
Examples 25-32, Comparative Examples 16-20:
A resin composition was obtained in the same manner as in the embodiment of the present invention except that various kinds of fine orange pigments were changed.
[0204]
Table 9 shows the production conditions and various properties of the obtained resin composition.
[0205]
[Table 9]

[0206]
【Effect of the invention】
The fine orange pigment according to the present invention is harmless, has improved chemical resistance and heat resistance, and has excellent transparency by using the fine orange pigment. Since a composition can be obtained, it is suitable as a color pigment for resins, paints, printing inks and the like.
[0207]
The paint and resin composition according to the present invention uses a fine orange pigment that is excellent in heat resistance and chemical resistance and is harmless. Therefore, it is an orange that is environmentally friendly and has excellent transparency. It is suitable as a color paint and a resin composition.

Claims (4)

Particle surfaces of hydrated iron oxide fine particles are, together with being coated with one or more selected from polysiloxane emissions represented by organosilane compounds or of 2 generated from alkoxysilane represented by 1, the organosilane compounds or polysiloxanes The amount of coating is 0.15 to 0.44% by weight in terms of Si with respect to the organosilane compound-coated hydrous iron oxide fine particle powder or the polysiloxane-coated hydrous iron oxide fine particle powder, and the organic red pigment adheres to the coating. The fine particles of the composite hydrous hydrated fine particles having an average major axis diameter of 0.0579 to 0.0919 μm, and the amount of the organic red pigment adhered is 5 to 25 parts by weight with respect to 100 parts by weight of the hydrated iron oxide fine particles. A fine orange pigment characterized by

 The particle surface of the hydrous iron oxide fine particle powder according to claim 1 is coated with an intermediate coating made of at least one selected from an aluminum hydroxide, an aluminum oxide, a silicon hydroxide and a silicon oxide. A fine orange pigment characterized by  3. A paint comprising the fine orange pigment according to claim 1 blended in a paint constituting base material.  A resin composition characterized by being colored using the fine orange pigment according to claim 1.