JP4691633B2 - Method for producing tin-containing granular magnetic oxide particles - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、錫含有粒状磁性酸化物粒子の製造方法に関し、詳しくは、黒色度が高く、磁化値が小さく、且つ、分散性に優れた錫含有粒状磁性酸化物粒子の製造方法に関する。本発明に係る錫含有粒状磁性酸化物粒子は、塗料用、印刷インキ用、ゴム・プラスチック用の着色顔料、磁性トナー用材料、磁性キヤリア用材料などとして有用である。
【０００２】
【従来の技術】
粒状磁性酸化物粒子は、黒色を呈しているため、塗料用、印刷インキ用、ゴム・プラスチック用の黒色着色顔料として広く使用されている。また、強磁性粒子であることから、樹脂中に混合分散させて複合体粒子とすることにより静電複写のための磁性トナーおよび磁性キヤリアとしても使用されている。
【０００３】
着色顔料を含有する塗膜の諸特性は、塗膜中における顔料の分散性に依存する。例えば、顔料のビヒクルや樹脂中の分散が良好であれば、色調が鮮明となるとともに、着色力、隠ぺい力等の材料粒子の特性も向上する。また、塗膜の光沢、鮮映性、機械的性質、塗膜の耐透気性なども良好となり、塗膜の耐久性が向上する。それ故、ビヒクルや樹脂に対する優れた分散性が要求されている。
【０００４】
また、静電複写機器の小型化、高速化などの高速性能に伴い、高濃度現像および高解像度が可能な磁性トナー及び磁性キヤリアが求められているが、これらの特性は、樹脂中に含有される磁性粒子の諸特性およびその分散性と密接に関係する。
【０００５】
例えば、高濃度現像を可能にするために、樹脂中の磁性粒子の含有量を大きくすると、磁性粒子の磁気的な凝集により現像した後の潜像上に磁性トナ―が凝集塊として存在するため、細かい潜像を忠実に再現することが難しく、高解像度の画が得られなくなる。また、樹脂中の磁性粒子の分散性が悪いと、磁性粒子が均一に分散されないために、磁性トナ―粒子に磁気的な偏りを生じたり、樹脂中の磁性粒子の含有量が少なくなる。その結果、高濃度現像を行うことが出来ず、且つ、高解像度の画も得られなくなる。
【０００６】
高画像濃度および高解像度を達成するためには、樹脂中に含まれる磁性粒子の含有量を多くしても磁気的な凝集力を生じない様に、磁性粒子の磁化値を出来るだけ小さくすると共に、樹脂中の磁性粒子の分散性を高くし、且つ、十分な黒色度を有する様に、粒状磁性粒子中のＦｅ2+の含有量をできるだけ多くすることも要求されている。
【０００７】
磁化値の小さい粒状磁性酸化物粒子は、ヘマタイトあるいはヘマタイト＋マグネタイトを２４．０〜９９．２重量％と、Ｓｎ化合物をＳｎ換算で０．８〜７６．０重量％と、−Ｃ−Ｃ−あるいは−Ｃ＝Ｃ−を分子中に有する液体状物質あるいは固体状物質を０．１〜４．０重量％とを混合し、得られた混合物を不活性ガス中で１２００〜１４５０℃で焼成して得られる（特開平７−１１５００９号公報）。しかしながら、この方法で得られる粒状磁性酸化物粒子は、１２００〜１４５０℃で焼成して得られる粒子であるため、フーバー式マラー法（ＪＩＳ Ｋ５１０１（１９９１）９．１）によりグラインドメーターを使用した顔料分散試験において１０ｍｍ以上の連続した線を３本以上発現した時の溝の深さの値が１００μｍであり、分散性が優れているとは言い難いものである。
【０００８】
また、分散性の良い磁性酸化物粒子は、第一鉄塩水溶液に珪酸塩およびＭｎ、Ｚｎ、Ｎｉ、Ｃｕ、Ｃｏ、Ｃｒ、Ｃｄ、Ａｌ、ＳｎおよびＭｇから選ばれる１種以上の金属塩を鉄元素に対して０．２〜４．０重量％となるように添加した後、水酸化ナトリウム等のアルカリ性水溶液を加え、得られた水酸化第一鉄を含む水溶液のｐＨを７以上に維持しながら空気を吹き込んで水酸化第一鉄を酸化して磁性酸化鉄種晶を生成させ、次いで硫酸第一鉄などの第一鉄塩水溶液を添加し、得られた水溶液のｐＨを６〜１０に維持しながら空気を吹き込んで磁性酸化鉄種晶を成長させることにより得られる（特開平１１−２４９３３５号公報）。しかしながら、当該公報には、Ｍｎ、Ｚｎ、Ｎｉ、Ｃｕ、Ｃｏ、Ｃｒ、Ｃｄ、Ａｌ、ＳｎおよびＭｇから選ばれる１種以上の金属塩の量が多くなると、得られる磁性酸化物粒子の分散性が低下すると示唆されている。
【０００９】
【発明が解決しようとする課題】
本発明の目的は、十分な黒色度を有し、磁化値の小さい、且つ、分散性の優れた粒状磁性酸化物粒子の製造方法を提供するにある。
【００１０】
【課題を解決するための手段】
本発明者らは、上記目的を達成すべく鋭意検討した結果、例えば、第一鉄塩水溶液と第一鉄に対してＳｎ換算で１０〜３０ｍｏｌ%の錫化合物水溶液とアルカリ性水溶液とを混合し、得られた鉄-錫含有沈殿物を含む懸濁液を水熱処理して得られる特定の錫含有粒状磁性酸化物粒子により、上記課題を解決出来ることを見い出し、本発明を完成するに至った。
【００１１】
本発明は、上記の知見に基づき完成されたものであり、その要旨は、下記の化学式で表されるスピネル型結晶から成り、Ｆｅ2+の含有量が１７〜２２重量％、格子定数が８．４１〜８．４９Å、印加磁界７９．６ｋＡ／ｍでの磁化値が２０〜５０Ａｍ2／ｋｇ、フーバー式マラー法（ＪＩＳ Ｋ５１０１（１９９１）９．１）によりグラインドメーターを使用した顔料分散試験において１０ｍｍ以上の連続した線を３本以上発現した時の溝の深さの値が４０μｍ以下である錫含有粒状磁性酸化物粒子の製造方法であって、第一鉄塩水溶液と第一鉄に対してＳｎ換算で１０〜３０ｍｏｌ%の錫化合物水溶液とアルカリ性水溶液とを混合し、得られた鉄-錫含有沈殿物を含む懸濁液を、１０１〜３００℃で０．５〜４８時間水熱処理することを特徴とする錫含有粒状磁性酸化物粒子の製造方法に存する。
【００１２】
【化２】
Ｆｅ3-xＳｎxＯ4
（式中、ｘは０．１４〜０．４８である）
【００１４】
【発明の実施の形態】
以下、本発明を説明する。本発明に係る錫含有粒状磁性酸化物粒子は、前記の化学式で表されるスピネル型結晶から成る。スピネル型結晶格子中のＳｎ元素の有無は、X線回折パターンより得られる格子定数のＳｎ含有量に対する変化を測定することにより確認できる。スピネル型結晶格子中にＳｎ元素を有していない場合は、磁化値の小さい粒状磁性粒子を得ることが出来ない。
【００１５】
錫含有粒状磁性酸化物粒子のＳｎ元素の含有量は、前記化学式に従い、７〜２２重量％（ｘ＝０．１４〜０．４８） 、好ましくは１０〜２０重量％である。Ｓｎ元素の含有量が７重量％未満の場合は、目的の磁化値を得ることが出来ない。Ｓｎ元素の含有量が２２重量％を超える場合は、粒状磁性酸化物粒子の製造過程で、Ｓｎ化合物が析出し、粒状磁性酸化物粒子の分散性や黒色度を悪化する。
【００１６】
錫含有粒状磁性酸化物粒子のＦｅ2+の含有量は、１７〜２２重量％、好ましくは１８〜２２重量％である。Ｆｅ2+含有量が１７重量％未満の場合は、粒状磁性酸化物粒子の黒色度が不十分である。Ｆｅ2+含有量が２２重量％を超える場合は、粒状磁性酸化物粒子としての黒色度は十分に高いものであるが、酸化安定性が悪く、空気中での取り扱いが困難となる。
【００１７】
錫含有粒状磁性酸化物粒子の格子定数は、８．４１〜８．４９Å、好ましくは、８．４３〜８．４８Åである。スピネル型結晶格子中に含有されるＳｎ元素量が多くなる程格子定数が大きくなる傾向にある。例えば、Ｓｎ元素の含有量が７．８重量％のとき、格子定数が８．４１Å程度であり、Ｓｎ元素の含有量が２１．７重量％のとき、格子定数が８．４９Å程度である。格子定数が８．４１Å未満の場合、粒状磁性酸化物粒子の黒色度が不十分であり、格子定数が８．４９Åを超えると、粒状磁性酸化物粒子の酸化安定性が悪くなる。
【００１８】
錫含有粒状磁性酸化物粒子の印加磁界７９．６ｋＡ／ｍでの磁化値は、２０〜５０Ａｍ2／ｋｇ、好ましくは２５〜４５Ａｍ2／ｋｇである。スピネル型結晶格子中に含有されるＳｎ元素の含有量が多くなる程磁化値が低下する傾向にあり、Ｓｎ元素の含有量が２１．７重量％のとき、磁化値が２０Ａｍ2／ｋｇ程度である。磁化値が２０Ａｍ2／ｋｇ未満の場合は、磁性トナーが飛散し易くなり、高解像度の画が得られなくなる。磁化値が５０Ａｍ2／ｋｇを超える場合は、磁気凝集力が大きく、ビヒクルや樹脂中における分散性が劣り、高濃度および高解像度画が得られなくなる。
【００１９】
錫含有粒状磁性酸化物粒子の分散性は、フーバー式マラー法（ＪＩＳ Ｋ５１０１（１９９１）９．１）によりグラインドメーターを使用した顔料分散試験において１０ｍｍ以上の連続した線が３本以上発現し始めた時の溝の深さの値で示す。本発明の錫含有粒状磁性酸化物粒子の１０ｍｍ以上の連続した線が３本以上発現し始めた時の溝の深さの値は、４０μｍ以下、好ましくは３０μｍ以下、より好ましくは２０μｍ以下である。１０ｍｍ以上の連続した線が３本以上発現し始めた時の溝の深さの値が４０μｍを超える場合は、ビヒクルや樹脂中における分散性が劣り、高濃度および高解像度画が得られなくなる。
【００２０】
錫含有粒状磁性酸化物粒子の黒色度は、ＪＩＳＫ５１０１（１９９１）６．１に記載の方法で得られたペーストを６ｍｉｌのフイルムアプリケーターを使用して、ミラーコート紙上に塗膜を形成し、分光測色計を使用してＪＩＳ Ｚ ８７２９により測色して、表色指数ａ*値で示す。本発明の錫含有粒状磁性酸化物粒子のａ*値は、通常＋１．５以下、好ましくは＋１．０以下、より好ましくは＋０．５以下である。ａ*値が＋１．５を超える場合には、赤味が強くなり十分な黒色度を有する粒子を得ることができないことがある。
【００２１】
錫含有粒状磁性酸化物粒子の平均粒子径は、通常０．１〜０．３μｍ、好ましくは０．１５〜０．２５μｍである。平均粒子径が０．１μｍ未満の場合は、磁性酸化物粒子相互間の凝集力が大きく分散性が困難となる傾向にある。平均粒子径が０．３μｍを超える場合は、磁性酸化物粒子の着色力が低下する傾向にある。磁性トナーでは、一個の磁性トナーに含まれる磁性酸化物粒子の個数が少なくなったり、また、磁性トナー粒子中の磁性酸化物粒子の分布に偏りが生じ易くなり、磁性トナーの帯電性能の均一性が損なわれることがある。
【００２２】
次に、本発明の錫含有粒状磁性酸化物粒子の製造方法について説明する。本発明の製造方法においては、先ず、第一鉄塩水溶液と第一鉄に対してＳｎ換算で１０〜３０ｍｏｌ%の錫化合物水溶液とアルカリ性水溶液とを混合する。この場合、第一鉄塩水溶液と第一鉄に対してＳｎ換算で１０〜３０ｍｏｌ%の錫化合物水溶液とを混合し、次いで得られた混合液にアルカリ性水溶液を添加することが好ましい。即ち、先ず、第一鉄塩水溶液と第一鉄に対してＳｎ換算で１０〜３０ｍｏｌ%の錫化合物水溶液とを混合して、鉄−錫混合溶液を得る。詳しくは、水に第一鉄塩（鉄元素換算で、通常０．１〜１０モル程度、好ましくは０．５〜５モル程度）を溶解する。別に、水またはアルコール水溶液中に錫化合物（鉄元素換算で、通常０．００１〜５モル程度、好ましくは０．５〜２モル程度）を溶解する。得られた第一鉄塩水溶液と錫化合物水溶液を混合して鉄−錫混合溶液を得る。
【００２３】
次いで、アルカリ性水溶液を、攪拌しながら鉄−錫混合溶液に徐々に滴下し、滴下後、室温下で数時間〜１日間程度攪拌して目的物である鉄−錫含有沈殿物を含む懸濁液を得る。添加されるアルカリ性水溶液の量は、鉄−錫混合溶液の鉄および錫に対して通常１当量以上で、その上限は好ましくは２．０当量、より好ましくは１．６当量である。
【００２４】
得られた鉄−錫含有沈殿物を含む懸濁液を水熱処理して目的生成物を得る。すなわち、水熱反応炉（例えば、オートクレーブ）を使用して鉄−錫含有沈殿物を含む懸濁液を水熱反応処理する。好ましくはアンモニウム塩または前記アルカリ性水溶液と同一のアルカリ金属の塩の存在下で行われる。生成する錫含有粒状磁性酸化物粒子の粒度分布を考慮すれば、アンモニウム塩またはアルカリ塩の存在量は、アルカリ性水溶液１モルに対して０．５〜１．５モルが好ましい。水熱反応の条件は特に限定されるものではないが、通常１０１〜３００℃程度、好ましくは２００〜２５０℃程度の温度で、通常０．５〜４８時間程度、好ましくは１〜１０時間程度である。反応終了後、残存する未反応原料を除去するために、反応生成物を水洗し、次いで濾過し、乾燥することより、下記の式で示される錫含有粒状磁性酸化物粒子を得る。
【００２５】
【化３】
Ｆｅ3-xＳｎxＯ4
（式中、ｘは０．１４〜０．４８である）
【００２６】
本発明の製造方法において使用する第一鉄塩水溶液としては、塩化第一鉄水溶液、硝酸第一鉄水溶液、硫酸第一鉄水溶液等が挙げられる。好ましくは硫酸第一鉄水溶液である。錫化合物水溶液としては、塩化第一錫水溶液、硝酸第一錫水溶液、硫酸第一錫水溶液等が挙げられる。好ましくは塩化第一錫水溶液である。
【００２７】
アルカリ性水溶液としては、水酸化リチウム水溶液、水酸化ナトリウム水溶液、水酸化カリウム水溶液、アンモニウム水溶液等が挙げらる。特に、水酸化ナトリウム水溶液が好ましい。これらは単独で使用してもまた２種以上を併用してもよい。
【００２８】
必要により使用するアンモニウム塩またはアルカリ塩は、水熱処理に先立って鉄−錫含有沈殿物を含む懸濁液中に存在させておけば良い。アルカリ塩としては、Ｌｉ塩、Ｎａ塩、Ｋ塩が挙げられる。上述のアルカリ性水溶液のアルカリ金属と同一のアルカリ金属の塩を使用した場合には、粒度分布の優れた錫含有粒状磁性酸化物粒子を得ることが出来る。
【００２９】
この様にして得られた錫含有粒状磁性酸化物粒子は、粒状磁性粒子中のＦｅ2+の含有量が大きく、十分な黒色度を有し、且つ、磁化値が小さいので磁気的な凝集力を生ぜず、更に、ビヒクルや樹脂に対する分散性も優れている。
【００３０】
【実施例】
以下、実施例により本発明を詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。
【００３１】
粒状磁性酸化物粒子全体のＦｅＯ含有量は、下記の化学分析法により求めた値で示した。すなわち、不活性ガス雰囲気下で、リン酸：硫酸が２：１（重量比）の割合の混合溶液２５ｍｌを粒状磁性酸化物粒子約０．５ｇに添加して溶解した。粒状磁性酸化物粒子が溶解した溶液を希釈し、該希釈溶液に指示薬としてジフェニルアミンスルホン酸を数滴加えた後、重クロム酸カリウム水溶液を用いて酸化還元滴定を行った。上記希釈液が紫色を呈した時を終点とし、該終点に至るまでに使用した重クロム酸カリウム水溶液の量から計算して求めた。
【００３２】
粒状磁性酸化物のＳｎ含有量は、「エネルギー分散型Ｘ線分析計 ＥＤＸ」（日立製作所社製）で測定した。
【００３３】
錫含有粒状磁性酸化物粒子の結晶相は、X線回折分析により測定した。化学組成はX線エネルギー分散スペクトル分析により評価した。
【００３４】
錫含有粒状磁性酸化物粒子の磁気特性は、「振動試料型磁力計 ＶＳＭ−３Ｓ−１５」（東英工業社製）を用いて外部磁場７９．６ｋＡ／ｍの下で測定した値で示した。
【００３５】
錫含有粒状磁性酸化物粒子の分散性は、試料１ｍｇとビヒクルとして印刷インキ用ロジン変性フェノール樹脂系ワニス１０ｍｇとをそれぞれフーバー式マラーの下部練り板の上に乗せ、ヘラで混ぜ合わせ、練り板上に帯状に広げ、フーバー式マラー法（ＪＩＳ Ｋ５１０１（１９９１）９．１）によりグラインドメーターを使用した顔料分散試験において１０ｍｍ以上の連続した線を３本以上発現し始めた時の溝の深さの値を測定した。
【００３６】
錫含有粒状磁性酸化物粒子の黒色度は、試料０．５ｇとヒマシ油１．５ｍｌ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、 該塗料片について、多光源分光測色計ＭＳＣ−ＩＳ−２Ｄ（スガ試験機株式会社製）を用いて、ＪＩＳ Ｚ ８７２９により測色して、表色指数ａ*値で示した。ここで、ａ*値は赤味の程度を表わし、ａ*値が小さいほど黒色度が優れていることを示す。
【００３７】
錫含有粒状磁性酸化物粒子の形状は、透過型電子顕微鏡（倍率２万倍）および走査型電子顕微鏡（倍率４万倍）により観察して判定した。粒状磁性酸化物粒子の平均粒子径は、透過型電子顕微鏡により撮影した写真（倍率１万倍）を４倍に拡大して、３００個についてマーチン径により求めた。
【００３８】
錫含有粒状磁性酸化物粒子の粒度分布は、上述の方法により求めた平均粒径（ｄ）と標準偏差（σ）から、式：変化係数（％）＝（σ／ｄ）ｘ１００により算出した変化係数で示した。変化係数の値が小さい程、粒度分布が優れていることを示し、変化係数が３０％以下あれば、粒度分布が良好であり、好ましくは２５％以下である。変化係数が３０％を超えると、粒度分布が悪く顔料としての分散性に劣り、種々の特性が損なわれることがある。
【００３９】
実施例１
塩化第一スズ２水和物４．０６ｇに１５０ｍｌの水を加え、攪拌して溶解した。別に、硫酸第一鉄７水和物４５．０ｇに１５０ｍｌの水を加え、攪拌して溶解した。両溶液を攪拌しながら混合し、Ｆｅ−Ｓｎ混合水溶液（Ｓｎ：Ｆｅ（モル比）＝１：９）を得た。水酸化ナトリウム２２．０ｇに水３００ｍｌを加えて溶解し、得られた水溶液を攪拌しながら、上記Ｆｅ−Ｓｎ混合水溶液に徐々に滴下し、滴下後、更に数時間攪拌してＦｅ−Ｓｎ含有沈殿物（Ｓｎ：Ｆｅ（モル比）＝１：９）を得た。得られたＦｅ−Ｓｎ含有沈殿物の懸濁液を水熱反応炉（オートクレーブ）中で、２２０℃で１時間水熱処理した。水熱処理終了後、生成物を水で洗浄して、過剰に存在する水酸化ナトリウムを除去し、濾過、乾燥して、粒状生成物を得た。
【００４０】
得られた粒状生成物は、八面体形状の微粒子であり、その組成はFe2.84Sn0.16O4であった。粒状生成物の平均粒子径は０．２３μｍで、格子定数は８．４１２Åで、Ｆｅ2+含有量は２１．４重量％で、Ｓｎ元素含有量は７．８重量％で、７９．６ｋＡ／ｍの磁場での磁化値は４８．５Ａｍ2／ｋｇで、黒色度ａ*値は＋０．３であった。分散性は、ＪＩＳ Ｋ５１０１（１９９１）の顔料分散試験法のフーバー式マラー法によりグラインドメーターを使用した顔料分散試験により評価した結果、溝の深さ２０μｍ以上には３本の１０ｍｍ以上連続した線の存在が全く認められなかった。得られた粒状生成物の変化係数は２８％であった。
【００４１】
実施例２
塩化第一スズ２水和物４．０６ｇに１５０ｍｌの水を加え、攪拌して溶解した。別に、硫酸第一鉄７水和物４５．０ｇに１５０ｍｌの水を加え、攪拌して溶解した。両溶液を攪拌しながら混合し、Ｆｅ−Ｓｎ混合水溶液（Ｓｎ：Ｆｅ（モル比）＝１：９）を得た。塩化ナトリウム３８．０ｇと水酸化ナトリウム２２．０ｇに水３００ｍｌを加えて溶解し、得られた水溶液を攪拌しながら、上記Ｆｅ−Ｓｎ混合水溶液に徐々に滴下し、滴下後、更に数時間攪拌してＦｅ−Ｓｎ含有沈殿物（Ｓｎ：Ｆｅ（モル比）＝１：９）を得た。得られたＦｅ−Ｓｎ含有沈殿物を含む懸濁液を水熱反応炉（オートクレーブ）中で、２２０℃で１時間水熱処理した。水熱処理終了後、生成物を水で洗浄して、過剰に存在する水酸化ナトリウムを除去し、濾過、乾燥して、粒状生成物を得た。
【００４２】
得られた粒状生成物は、八面体形状の微粒子であり、その組成はFe2.84Sn0.16O4であった。粒状生成物の平均粒子径は０．２３μｍで、格子定数は８．４１２Åで、Ｆｅ2+含有量は２１．４重量％で、Ｓｎ元素含有量は７．８重量％で、７９．６ｋＡ／ｍの磁場での磁化値は４８．５Ａｍ2／ｋｇで、黒色度ａ*値は＋０．３であった。分散性は、ＪＩＳ Ｋ５１０１（１９９１）の顔料分散試験法のフーバー式マラー法によりグラインドメーターを使用した顔料分散試験により評価した結果、溝の深さ２０μｍ以上には３本の１０ｍｍ以上連続した線の存在が全く認められなかった。得られた粒状生成物の変化係数は２２％であった。
【００４３】
実施例３
無水塩化第一スズ６．８３ｇに１５０ｍｌのメタノールを加え、攪拌して溶解した。別に、硫酸第一鉄７水和物４０．０ｇに１５０ｍｌの水を加え、攪拌して溶解した。両溶液を攪拌しながら混合し、Ｆｅ−Ｓｎ混合水溶液（Ｓｎ：Ｆｅ（モル比）＝２：８）を得た。塩化ナトリウム３８．０ｇと水酸化ナトリウム２２．０ｇに水３００ｍｌを加えて溶解し、得られた水溶液を攪拌しながら、上記Ｆｅ−Ｓｎ混合物に徐々に滴下し、滴下後、更に数時間攪拌してＦｅ−Ｓｎ含有沈殿物Ｓｎ：Ｆｅ（モル比）＝２：８）を得た。得られたＦｅ−Ｓｎ含有沈殿物の懸濁液を水熱反応炉（オートクレーブ）中で、２２０℃で１時間水熱処理した。水熱処理終了後、生成物を水で洗浄して、過剰に存在する水酸化ナトリウム及び他のアルカリ塩類を除去し、濾過、乾燥して、粒状生成物を得た。
【００４４】
得られた粒状生成物は、八面体形状の微粒子であり、その組成はFe2.65Sn0.35O4であった。粒状生成物の平均粒子径は０．１８μｍで、格子定数は８．４７０Åで、Ｆｅ2+含有量は２０．５重量％で、Ｓｎ元素含有量は１６．４重量％で、７９．６ｋＡ／ｍの磁場での磁化値は３５．１Ａｍ2／ｋｇで、黒色度ａ*値は；０．５であった。分散性は、ＪＩＳ Ｋ５１０１−１９９１の顔料分散試験法のフーバー式マラー法により評価した結果、３０μｍ以上には１０ｍｍ以上の連続した線の存在が全く認められなかった。得られた粒状生成物の変化係数は２１％であった。
【００４５】
実施例４
無水塩化第一スズ１０．２３ｇに１５０ｍｌのメタノールを加え、攪拌して溶解した。別に、硫酸第一鉄７水和物３５．０ｇに１５０ｍｌの水を加え、攪拌して溶解した。両溶液を攪拌しながら混合し、Ｆｅ−Ｓｎ混合物（Ｓｎ：Ｆｅ（モル比）＝３：７）を得た。塩化ナトリウム３８．０ｇと水酸化ナトリウム２２．０ｇに水３００ｍｌを加えて溶解し、得られた水溶液を攪拌しながら、上記Ｆｅ−Ｓｎ混合物に徐々に滴下し、滴下後、更に数時間攪拌してＦｅ−Ｓｎ共沈物Ｓｎ：Ｆｅ（モル比）＝３：７）を得た。得られたＦｅ−Ｓｎ共沈物を水熱反応炉（オートクレーブ）中で、２２０℃で１時間水熱処理した。水熱処理終了後、生成物を水で洗浄して、過剰に存在する水酸化ナトリウム及び他のアルカリ塩類を除去し、濾過、乾燥して、粒状生成物を得た。
【００４６】
得られた粒状生成物は、八面体形状の微粒子であり、その組成はFe2.52Sn0.48O4であった。粒状生成物の平均粒子径は０．１３μｍで、格子定数は８．４８７Åで、Ｆｅ2+含有量は１８．１重量％で、Ｓｎ元素含有量は２１．８重量％で、７９．６ｋＡ／ｍの磁場での磁化値は２１．５Ａｍ2／ｋｇで、黒色度ａ*値は＋０．７であった。分散性は、ＪＩＳ Ｋ５１０１−１９９１の顔料分散試験法のフーバー式マラー法により評価した結果、３０μｍ以上には１０ｍｍ以上の連続した線の存在が全く認められなかった。得られた粒状生成物の変化係数は２３％であった。
【００４７】
【発明の効果】
錫含有粒状磁性酸化物粒子は、Ｆｅ2+の含有量が大きく、粒度分布に優れ且つ十分な黒色度を有し、磁化値が小さいので磁気的な凝集力を生ずることがなく、ビヒクルや樹脂に対する分散性も優れている。それ故、塗料用、印刷インキ用、ゴム・プラスチック用の着色顔料、磁性トナー用材料、磁性キヤリア用材料などとして有用である。また、比較的低い温度で錫含有粒状磁性酸化物粒子を製造することが出来るので、工業的に有益な方法である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of manufacturing a tin-containing granular magnetic oxide particles, particularly, high blackness, the magnetization value is small, and a method for producing a superior tin-containing granular magnetic oxide particles in dispersion. The tin-containing granular magnetic oxide particles according to the present invention are useful as coloring pigments for paints, printing inks, rubber / plastics, magnetic toner materials, magnetic carrier materials, and the like.
[0002]
[Prior art]
Since the granular magnetic oxide particles are black, they are widely used as black coloring pigments for paints, printing inks, rubbers and plastics. Further, since it is a ferromagnetic particle, it is also used as a magnetic toner and a magnetic carrier for electrostatic copying by mixing and dispersing in a resin to form composite particles.
[0003]
Various properties of the coating film containing the color pigment depend on the dispersibility of the pigment in the coating film. For example, if the dispersion of the pigment in the vehicle or resin is good, the color tone becomes clear and the characteristics of the material particles such as coloring power and hiding power are improved. Further, the gloss, sharpness, mechanical properties, and air resistance of the coating film are also improved, and the durability of the coating film is improved. Therefore, excellent dispersibility for vehicles and resins is required.
[0004]
In addition, along with high speed performance such as miniaturization and high speed of electrostatic copying machines, magnetic toner and magnetic carrier capable of high density development and high resolution are required, but these characteristics are contained in the resin. It is closely related to the properties and dispersibility of magnetic particles.
[0005]
For example, if the content of magnetic particles in the resin is increased in order to enable high-density development, the magnetic toner exists as an aggregate on the latent image after development due to magnetic aggregation of the magnetic particles. It is difficult to faithfully reproduce a fine latent image, and a high-resolution image cannot be obtained. Further, if the dispersibility of the magnetic particles in the resin is poor, the magnetic particles are not uniformly dispersed, so that the magnetic toner particles are magnetically biased or the content of the magnetic particles in the resin is reduced. As a result, high density development cannot be performed, and high resolution images cannot be obtained.
[0006]
In order to achieve high image density and high resolution, the magnetization value of the magnetic particles should be made as small as possible so that magnetic cohesion does not occur even if the content of the magnetic particles contained in the resin is increased. It is also required to increase the content of Fe 2+ in the granular magnetic particles as much as possible so as to increase the dispersibility of the magnetic particles in the resin and to have sufficient blackness .
[0007]
The granular magnetic oxide particles having a small magnetization value include 24.0 to 99.2% by weight of hematite or hematite + magnetite, 0.8 to 76.0% by weight of Sn compound in terms of Sn, and —C—C— Alternatively, a liquid substance or a solid substance having —C═C— in the molecule is mixed with 0.1 to 4.0% by weight, and the obtained mixture is fired at 1200 to 1450 ° C. in an inert gas. (Japanese Patent Laid-Open No. 7-115009). However, since the granular magnetic oxide particles obtained by this method are particles obtained by firing at 1200 to 1450 ° C., a pigment using a grindometer according to the Hoover-type Muller method (JIS K5101 (1991) 9.1). In the dispersion test, the value of the groove depth when 3 or more continuous lines of 10 mm or more are developed is 100 μm, and it is difficult to say that the dispersibility is excellent.
[0008]
In addition, the magnetic oxide particles having good dispersibility include a silicate and one or more metal salts selected from Mn, Zn, Ni, Cu, Co, Cr, Cd, Al, Sn, and Mg in a ferrous salt aqueous solution. After adding 0.2 to 4.0% by weight with respect to iron element, an alkaline aqueous solution such as sodium hydroxide is added, and the pH of the obtained aqueous solution containing ferrous hydroxide is maintained at 7 or more. While blowing air, the ferrous hydroxide was oxidized to form a magnetic iron oxide seed crystal, and then an aqueous ferrous salt solution such as ferrous sulfate was added, and the pH of the obtained aqueous solution was adjusted to 6-10. The magnetic iron oxide seed crystal is grown by blowing air while maintaining the temperature (Japanese Patent Laid-Open No. 11-249335). However, in this publication, when the amount of one or more metal salts selected from Mn, Zn, Ni, Cu, Co, Cr, Cd, Al, Sn, and Mg increases, the dispersibility of the obtained magnetic oxide particles Has been suggested to decline.
[0009]
[Problems to be solved by the invention]
An object of the present invention has a sufficient degree of blackness, a small magnetization, and is to provide a method for producing a dispersion having excellent granular magnetic oxide particles.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors, for example, mixed a 10-30 mol% tin compound aqueous solution and an alkaline aqueous solution in terms of Sn with respect to the ferrous salt aqueous solution and ferrous iron, It has been found that the above problems can be solved by specific tin-containing granular magnetic oxide particles obtained by hydrothermally treating the obtained suspension containing the iron-tin-containing precipitate, and the present invention has been completed.
[0011]
The present invention has been completed based on the above findings, and the gist of the present invention consists of spinel crystals represented by the following chemical formula, the content of Fe 2+ is 17 to 22% by weight, and the lattice constant is 8 In a pigment dispersion test using a grindometer according to the Hoover-type Muller method (JIS K5101 (1991) 9.1) with a magnetization value of 20 to 50 Am 2 / kg at an applied magnetic field of 79.6 kA / m at 41 to 8.49 mm. A method for producing tin- containing granular magnetic oxide particles having a groove depth value of 40 μm or less when three or more continuous lines of 10 mm or more are developed , wherein the ferrous salt aqueous solution and ferrous iron are used. Then, 10-30 mol% tin compound aqueous solution and alkaline aqueous solution in terms of Sn are mixed, and the resulting suspension containing the iron-tin-containing precipitate is hydrothermally treated at 101-300 ° C. for 0.5-48 hours. With features It consists in the manufacturing method of that tin-containing granular magnetic oxide particles.
[0012]
[Chemical 2]
Fe 3-x Sn x O 4
(Wherein x is 0.14 to 0.48)
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below. The tin-containing granular magnetic oxide particles according to the present invention consist of spinel crystals represented by the above chemical formula. The presence or absence of Sn element in the spinel crystal lattice can be confirmed by measuring the change of the lattice constant obtained from the X-ray diffraction pattern with respect to the Sn content. When the Sn element is not contained in the spinel crystal lattice, granular magnetic particles having a small magnetization value cannot be obtained.
[0015]
The content of Sn element in the tin-containing granular magnetic oxide particles is 7 to 22% by weight (x = 0.14 to 0.48), preferably 10 to 20% by weight, according to the chemical formula. If the Sn element content is less than 7% by weight, the desired magnetization value cannot be obtained. When the content of Sn element exceeds 22% by weight, the Sn compound is precipitated in the production process of the granular magnetic oxide particles, and the dispersibility and blackness of the granular magnetic oxide particles are deteriorated.
[0016]
The content of Fe 2+ in the tin-containing granular magnetic oxide particles is 17 to 22% by weight, preferably 18 to 22% by weight. When the Fe 2+ content is less than 17% by weight, the blackness of the granular magnetic oxide particles is insufficient. When the Fe 2+ content exceeds 22% by weight, the blackness as the granular magnetic oxide particles is sufficiently high, but the oxidation stability is poor and handling in air becomes difficult.
[0017]
The lattice constant of the tin-containing granular magnetic oxide particles is 8.41-8.49 mm, preferably 8.43-8.48 mm. As the amount of Sn element contained in the spinel crystal lattice increases, the lattice constant tends to increase. For example, when the Sn element content is 7.8% by weight, the lattice constant is about 8.41%, and when the Sn element content is 21.7% by weight, the lattice constant is about 8.49%. When the lattice constant is less than 8.41Å, the blackness of the granular magnetic oxide particles is insufficient, and when the lattice constant exceeds 8.49Å, the oxidation stability of the granular magnetic oxide particles is deteriorated.
[0018]
The magnetization value of the tin-containing granular magnetic oxide particles at an applied magnetic field of 79.6 kA / m is 20 to 50 Am 2 / kg, preferably 25 to 45 Am 2 / kg. The magnetization value tends to decrease as the content of Sn element contained in the spinel crystal lattice increases. When the content of Sn element is 21.7 wt%, the magnetization value is about 20 Am 2 / kg. is there. When the magnetization value is less than 20 Am 2 / kg, the magnetic toner is easily scattered and a high-resolution image cannot be obtained. When the magnetization value exceeds 50 Am 2 / kg, the magnetic cohesive force is large, the dispersibility in the vehicle or the resin is poor, and a high density and high resolution image cannot be obtained.
[0019]
As for the dispersibility of the tin-containing granular magnetic oxide particles, three or more continuous lines of 10 mm or more began to appear in a pigment dispersion test using a grindometer by the Hoover-type Muller method (JIS K5101 (1991) 9.1). It is indicated by the value of the depth of the groove at the time. The depth value of the groove when three or more continuous lines of 10 mm or more of the tin-containing granular magnetic oxide particles of the present invention begin to appear is 40 μm or less, preferably 30 μm or less, more preferably 20 μm or less. . When the depth value of the groove when three or more continuous lines of 10 mm or more begin to appear exceeds 40 μm, the dispersibility in the vehicle or the resin is inferior, and a high density and high resolution image cannot be obtained.
[0020]
The blackness of the tin-containing granular magnetic oxide particles was measured by forming a coating film on a mirror-coated paper from a paste obtained by the method described in JIS K5101 (1991) 6.1 using a 6 mil film applicator, and performing spectroscopic measurement. The color is measured according to JIS Z 8729 using a colorimeter, and is indicated by the color index a * value. The a * value of the tin-containing granular magnetic oxide particles of the present invention is usually +1.5 or less, preferably +1.0 or less, more preferably +0.5 or less. When the a * value exceeds +1.5, redness becomes strong and particles having sufficient blackness may not be obtained.
[0021]
The average particle diameter of the tin-containing granular magnetic oxide particles is usually 0.1 to 0.3 μm, preferably 0.15 to 0.25 μm. When the average particle diameter is less than 0.1 μm, the cohesive force between the magnetic oxide particles tends to be large and dispersibility tends to be difficult. When the average particle diameter exceeds 0.3 μm, the coloring power of the magnetic oxide particles tends to decrease. In the magnetic toner, the number of magnetic oxide particles contained in one magnetic toner is reduced, and the distribution of the magnetic oxide particles in the magnetic toner particles tends to be biased. May be damaged.
[0022]
Next, the manufacturing method of the tin containing granular magnetic oxide particle of this invention is demonstrated. In the production method of the present invention, first, a 10-30 mol% tin compound aqueous solution and an alkaline aqueous solution in terms of Sn are mixed with respect to the ferrous salt aqueous solution and ferrous iron. In this case, it is preferable to mix 10-30 mol% tin compound aqueous solution in Sn conversion with respect to ferrous salt aqueous solution and ferrous iron, and then add alkaline aqueous solution to the obtained liquid mixture. That is, first, an iron-tin mixed solution is obtained by mixing a ferrous salt aqueous solution and a 10-30 mol% tin compound aqueous solution in terms of Sn with respect to ferrous iron. Specifically, a ferrous salt (usually about 0.1 to 10 mol, preferably about 0.5 to 5 mol in terms of iron element) is dissolved in water. Separately, a tin compound (usually about 0.001 to 5 mol, preferably about 0.5 to 2 mol in terms of iron element) is dissolved in water or an aqueous alcohol solution. The obtained ferrous salt aqueous solution and tin compound aqueous solution are mixed to obtain an iron-tin mixed solution.
[0023]
Subsequently, the alkaline aqueous solution is gradually dropped into the iron-tin mixed solution while stirring, and after the dropping, the suspension containing the target iron-tin-containing precipitate is stirred at room temperature for about several hours to one day. Get. The amount of the alkaline aqueous solution to be added is usually 1 equivalent or more with respect to iron and tin in the iron-tin mixed solution, and the upper limit is preferably 2.0 equivalents, more preferably 1.6 equivalents.
[0024]
The suspension containing the obtained iron-tin-containing precipitate is hydrothermally treated to obtain the desired product. That is, a suspension containing an iron-tin-containing precipitate is subjected to a hydrothermal reaction treatment using a hydrothermal reactor (for example, an autoclave). It is preferably carried out in the presence of an ammonium salt or the same alkali metal salt as the alkaline aqueous solution. Considering the particle size distribution of the tin-containing granular magnetic oxide particles to be produced, the amount of the ammonium salt or alkali salt is preferably 0.5 to 1.5 mol with respect to 1 mol of the alkaline aqueous solution. The conditions for the hydrothermal reaction are not particularly limited, but are usually about 101 to 300 ° C., preferably about 200 to 250 ° C., usually about 0.5 to 48 hours, preferably about 1 to 10 hours. is there. After the reaction is completed, in order to remove the remaining unreacted raw material, the reaction product is washed with water, then filtered and dried to obtain tin-containing granular magnetic oxide particles represented by the following formula.
[0025]
[Chemical 3]
Fe 3-x Sn x O 4
(Wherein x is 0.14 to 0.48)
[0026]
Examples of the ferrous salt aqueous solution used in the production method of the present invention include ferrous chloride aqueous solution, ferrous nitrate aqueous solution, and ferrous sulfate aqueous solution. A ferrous sulfate aqueous solution is preferred. Examples of the tin compound aqueous solution include stannous chloride aqueous solution, stannous nitrate aqueous solution, and stannous sulfate aqueous solution. A stannous chloride aqueous solution is preferred.
[0027]
Examples of the alkaline aqueous solution include an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonium solution. In particular, an aqueous sodium hydroxide solution is preferred. These may be used alone or in combination of two or more.
[0028]
If necessary, the ammonium salt or alkali salt may be present in the suspension containing the iron-tin-containing precipitate prior to the hydrothermal treatment. Examples of the alkali salt include Li salt, Na salt, and K salt. When the same alkali metal salt as the alkali metal in the alkaline aqueous solution is used, tin-containing granular magnetic oxide particles having an excellent particle size distribution can be obtained.
[0029]
The tin-containing granular magnetic oxide particles thus obtained have a large content of Fe 2+ in the granular magnetic particles, a sufficient blackness, and a small magnetization value, so that the magnetic cohesive force Furthermore, it has excellent dispersibility in vehicles and resins.
[0030]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded.
[0031]
The FeO content of the entire granular magnetic oxide particles was indicated by the value obtained by the following chemical analysis method. That is, under an inert gas atmosphere, 25 ml of a mixed solution of phosphoric acid: sulfuric acid in a ratio of 2: 1 (weight ratio) was added to about 0.5 g of granular magnetic oxide particles and dissolved. The solution in which the granular magnetic oxide particles were dissolved was diluted, and after adding several drops of diphenylamine sulfonic acid as an indicator to the diluted solution, oxidation-reduction titration was performed using an aqueous potassium dichromate solution. The end point was when the diluted solution was purple, and the amount was calculated from the amount of the aqueous potassium dichromate solution used to reach the end point.
[0032]
The Sn content of the granular magnetic oxide was measured with an “energy dispersive X-ray analyzer EDX” (manufactured by Hitachi, Ltd.).
[0033]
The crystal phase of the tin-containing granular magnetic oxide particles was measured by X-ray diffraction analysis. The chemical composition was evaluated by X-ray energy dispersion spectrum analysis.
[0034]
The magnetic characteristics of the tin-containing granular magnetic oxide particles are shown by values measured under an external magnetic field of 79.6 kA / m using a “vibrating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.). .
[0035]
The dispersibility of the tin-containing granular magnetic oxide particles is as follows: 1 mg of the sample and 10 mg of rosin-modified phenolic resin varnish for printing ink as a vehicle are placed on the lower kneading plate of the Hoover type muller and mixed with a spatula. The groove depth when three or more continuous lines of 10 mm or more began to appear in a pigment dispersion test using a grindometer according to the Hoover-type Muller method (JIS K5101 (1991) 9.1). The value was measured.
[0036]
The blackness of the tin-containing granular magnetic oxide particles is obtained by kneading 0.5 g of a sample and 1.5 ml of castor oil with a Hoover-type Mahler to form a paste, adding 4.5 g of clear lacquer to the paste, kneading, and forming a paint. An application piece (coating thickness: about 30 μm) coated on a cast-coated paper using a 6 mil applicator was prepared, and the multi-light source spectrophotometer MSC-IS-2D (manufactured by Suga Test Instruments Co., Ltd.) Was measured in accordance with JIS Z 8729 and indicated by a color index a * value. Here, the a * value represents the degree of redness, and the smaller the a * value, the better the blackness.
[0037]
The shape of the tin-containing granular magnetic oxide particles was determined by observing with a transmission electron microscope (magnification 20,000 times) and a scanning electron microscope (magnification 40,000 times). The average particle diameter of the granular magnetic oxide particles was obtained by expanding the photograph taken with a transmission electron microscope (magnification 10,000 times) by 4 times and determining the Martin diameter of 300 particles.
[0038]
The particle size distribution of the tin-containing granular magnetic oxide particles is a change calculated from the average particle diameter (d) and standard deviation (σ) obtained by the above-described method according to the formula: change coefficient (%) = (σ / d) × 100 Indicated by coefficient. The smaller the change coefficient value, the better the particle size distribution. If the change coefficient is 30% or less, the particle size distribution is good, preferably 25% or less. When the change coefficient exceeds 30%, the particle size distribution is poor and the dispersibility as a pigment is inferior, and various properties may be impaired.
[0039]
Example 1
150 ml of water was added to 4.06 g of stannous chloride dihydrate and dissolved by stirring. Separately, 150 ml of water was added to 45.0 g of ferrous sulfate heptahydrate, and dissolved by stirring. Both solutions were mixed with stirring to obtain an Fe—Sn mixed aqueous solution (Sn: Fe (molar ratio) = 1: 9). 300 ml of water was added to 22.0 g of sodium hydroxide and dissolved, and the resulting aqueous solution was gradually added dropwise to the Fe—Sn mixed aqueous solution while stirring. The product (Sn: Fe (molar ratio) = 1: 9) was obtained. The obtained suspension of the Fe—Sn-containing precipitate was hydrothermally treated at 220 ° C. for 1 hour in a hydrothermal reactor (autoclave). After completion of the hydrothermal treatment, the product was washed with water to remove excess sodium hydroxide, filtered and dried to obtain a granular product.
[0040]
The obtained granular product was octahedral fine particles, and its composition was Fe 2.84 Sn 0.16 O 4 . The average particle size of the granular product is 0.23 μm, the lattice constant is 8.412 mm, the Fe 2+ content is 21.4 wt%, the Sn element content is 7.8 wt%, and 79.6 kA / The magnetization value in a magnetic field of m was 48.5 Am 2 / kg, and the blackness a * value was +0.3. The dispersibility was evaluated by a pigment dispersion test using a grindometer according to the Hoover-type Muller method of the pigment dispersion test method of JIS K5101 (1991), and as a result, three continuous lines of 10 mm or more were formed at a groove depth of 20 μm or more. Existence was not recognized at all. The coefficient of change of the obtained granular product was 28%.
[0041]
Example 2
150 ml of water was added to 4.06 g of stannous chloride dihydrate and dissolved by stirring. Separately, 150 ml of water was added to 45.0 g of ferrous sulfate heptahydrate, and dissolved by stirring. Both solutions were mixed with stirring to obtain an Fe—Sn mixed aqueous solution (Sn: Fe (molar ratio) = 1: 9). 300 ml of water was added to 38.0 g of sodium chloride and 22.0 g of sodium hydroxide to dissolve, and the resulting aqueous solution was gradually added dropwise to the Fe-Sn mixed aqueous solution while stirring. After the addition, the mixture was further stirred for several hours. Thus, a Fe—Sn-containing precipitate (Sn: Fe (molar ratio) = 1: 9) was obtained. The obtained suspension containing the Fe—Sn-containing precipitate was hydrothermally treated at 220 ° C. for 1 hour in a hydrothermal reactor (autoclave). After completion of the hydrothermal treatment, the product was washed with water to remove excess sodium hydroxide, filtered and dried to obtain a granular product.
[0042]
The obtained granular product was octahedral fine particles, and its composition was Fe 2.84 Sn 0.16 O 4 . The average particle size of the granular product is 0.23 μm, the lattice constant is 8.412 mm, the Fe 2+ content is 21.4 wt%, the Sn element content is 7.8 wt%, and 79.6 kA / The magnetization value in a magnetic field of m was 48.5 Am 2 / kg, and the blackness a * value was +0.3. The dispersibility was evaluated by a pigment dispersion test using a grindometer according to the Hoover-type Muller method of the pigment dispersion test method of JIS K5101 (1991), and as a result, three continuous lines of 10 mm or more were formed at a groove depth of 20 μm or more. Existence was not recognized at all. The change coefficient of the obtained granular product was 22%.
[0043]
Example 3
150 ml of methanol was added to 6.83 g of anhydrous stannous chloride and dissolved by stirring. Separately, 150 ml of water was added to 40.0 g of ferrous sulfate heptahydrate, and dissolved by stirring. Both solutions were mixed with stirring to obtain a Fe—Sn mixed aqueous solution (Sn: Fe (molar ratio) = 2: 8). 300 ml of water was added to 38.0 g of sodium chloride and 22.0 g of sodium hydroxide to dissolve, and the resulting aqueous solution was gradually added dropwise to the Fe-Sn mixture while stirring. After the addition, the mixture was further stirred for several hours. Fe-Sn-containing precipitate Sn: Fe (molar ratio) = 2: 8) was obtained. The obtained suspension of the Fe—Sn-containing precipitate was hydrothermally treated at 220 ° C. for 1 hour in a hydrothermal reactor (autoclave). After completion of the hydrothermal treatment, the product was washed with water to remove excess sodium hydroxide and other alkali salts, filtered and dried to obtain a granular product.
[0044]
The obtained granular product was octahedral fine particles, and its composition was Fe 2.65 Sn 0.35 O 4 . The average particle size of the granular product is 0.18 μm, the lattice constant is 8.470 mm, the Fe 2+ content is 20.5 wt%, the Sn element content is 16.4 wt%, and 79.6 kA / The magnetization value in a magnetic field of m was 35.1 Am 2 / kg, and the blackness a * value was 0.5. The dispersibility was evaluated by the Hoover-Muller method of the pigment dispersion test method of JIS K5101-1991. As a result, no continuous line of 10 mm or more was observed at 30 μm or more. The change coefficient of the obtained granular product was 21%.
[0045]
Example 4
150 ml of methanol was added to 10.23 g of anhydrous stannous chloride and dissolved by stirring. Separately, 150 ml of water was added to 35.0 g of ferrous sulfate heptahydrate and dissolved by stirring. Both solutions were mixed with stirring to obtain a Fe—Sn mixture (Sn: Fe (molar ratio) = 3: 7). 300 ml of water was added to 38.0 g of sodium chloride and 22.0 g of sodium hydroxide to dissolve, and the resulting aqueous solution was gradually added dropwise to the Fe-Sn mixture while stirring. After the addition, the mixture was further stirred for several hours. Fe—Sn coprecipitate Sn: Fe (molar ratio) = 3: 7) was obtained. The obtained Fe—Sn coprecipitate was hydrothermally treated at 220 ° C. for 1 hour in a hydrothermal reactor (autoclave). After completion of the hydrothermal treatment, the product was washed with water to remove excess sodium hydroxide and other alkali salts, filtered and dried to obtain a granular product.
[0046]
The obtained granular product was octahedral fine particles, and its composition was Fe 2.52 Sn 0.48 O 4 . The average particle size of the granular product is 0.13 μm, the lattice constant is 8.487%, the Fe 2+ content is 18.1 wt%, the Sn element content is 21.8 wt%, and 79.6 kA / The magnetization value in a magnetic field of m was 21.5 Am 2 / kg, and the blackness a * value was +0.7. The dispersibility was evaluated by the Hoover-Muller method of the pigment dispersion test method of JIS K5101-1991. As a result, no continuous line of 10 mm or more was observed at 30 μm or more. The change coefficient of the obtained granular product was 23%.
[0047]
【The invention's effect】
Tin-containing granular magnetic oxide particles have a large Fe 2+ content, excellent particle size distribution, sufficient blackness, and a small magnetization value, so that no magnetic cohesion is produced, and vehicles and resins Dispersibility with respect to is also excellent. Therefore, it is useful as a color pigment for paints, printing inks, rubbers and plastics, magnetic toner materials, magnetic carrier materials, and the like. Further, since tin-containing granular magnetic oxide particles can be produced at a relatively low temperature, this is an industrially useful method.
Claims (4)
【化１】
Ｆｅ3-xＳｎxＯ4
（式中、ｘは０．１４〜０．４８である）It consists of a spinel type crystal represented by the following chemical formula, the Fe 2+ content is 17-22 wt%, the lattice constant is 8.41-8.49%, and the magnetization value is 20 at an applied magnetic field of 79.6 kA / m. The depth value of the groove when 3 or more continuous lines of 10 mm or more are expressed in a pigment dispersion test using a grindometer by the Hoover-type Muller method (JISK5101 (1991) 9.1) by -50 Am 2 / kg A method for producing tin-containing granular magnetic oxide particles having a particle size of 40 μm or less, comprising mixing an aqueous ferrous salt solution and an aqueous tin compound solution of 10 to 30 mol% in terms of Sn with respect to ferrous iron, and an alkaline aqueous solution. A method for producing tin-containing granular magnetic oxide particles, comprising subjecting the suspension containing the iron-tin-containing precipitate to hydrothermal treatment at 101 to 300 ° C for 0.5 to 48 hours.
[Chemical 1]
Fe 3-x Sn x O 4
(Wherein x is 0.14 to 0.48)
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| JP2000-154247 | 2000-05-25 | ||
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60122726A (en) * | 1983-12-06 | 1985-07-01 | Central Glass Co Ltd | Manufacture of fine particle of magneto plumboferrite by wet process |
| JPH07101731A (en) * | 1993-09-30 | 1995-04-18 | Toda Kogyo Corp | Granular magnetite particle powder and its production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60122726A (en) * | 1983-12-06 | 1985-07-01 | Central Glass Co Ltd | Manufacture of fine particle of magneto plumboferrite by wet process |
| JPH07101731A (en) * | 1993-09-30 | 1995-04-18 | Toda Kogyo Corp | Granular magnetite particle powder and its production |
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