JP4155448B2 - Method for producing slurry containing red phosphorus particles and method for producing stabilized red phosphorus - Google Patents

Description

【００７９】
なお、粒度分布は、レーザー回折式粒度測定装置（セイシン企業社製、形式ＬＭＳ−２４型）により測定した。
鉄の含有量は酸分解チオグリコール酸吸光光度法より測定した。
黄燐はベンゼン抽出後、リン−バナジウムモリブデン酸吸光光度法により測定した。
【００８０】
実施例１
実施例１では、図２の実験装置を用いて実験を行った。この実験装置は、粗粒の赤燐粒子を含有するスラリーを貯蔵した容器１、湿式粉砕機のビーズミル２、ビーズミル２から排出されるスラリーを一時的に貯蔵するための容器３、２機の液体サイクロン４−１及び４−２、液体サイクロンの上部から排出された溶液を貯蔵するための上部容器５及び液体サイクロンの下部から排出された溶液を貯蔵するための下部容器６とを備える。
【００８１】
（第一工程）
上記の塊状赤燐１０ｋｇを水１００００ｋｇに分散させたスラリーを調製し、図２の容器１に貯蔵した。
次いで、粒径０．６ｍｍφのガラスビーズ６ｋｇを格納した容量５Ｌのボールミル（アイメックス社製；形式 ＮＶＭ５）２に、上記で調製したスラリーを供給し、湿式粉砕処理を行った。湿式粉砕処理後に、容器３に貯蔵された赤燐粒子を含有するスラリーの諸物性を表２に示す。
湿式粉砕処理条件は、原料スラリーのチャージ量３Ｌ／分、ローター回転数８００ｒｐｍで行った。
【００８２】
なお、各粒子の含有量、鉄及び黄燐の含有量は、スラリーの一部を固液分離し、乾燥した赤燐粉末中に含まれる含有量を示す。また、粒度特性、鉄と黄燐の含有量は前記と同様な方法で求めた。
【００８３】
【表２】

【００８４】
（第二工程）
第一工程後のスラリー５００ｋｇを液体サイクロン（三条鉄工社製）４−１及び４−２に供給した。液体サイクロン４−２のボトム部から排出された下部容器６に貯蔵されたスラリーの諸物性及び処理に要した時間と、５μｍ未満の赤燐粒子の除去率を表３に示す。
【００８５】
５μｍ未満の赤燐粒子の除去率は、下記計算式（１）により求めた。
【００８６】
【数１】

【００８７】
（式中のαは液体サイクロンに供給前の赤燐粒子全体量に占める５μｍ未満の粒子の含有量（重量％）、βは液体サイクロン処理後の赤燐粒子全体量に占める５μｍ未満の粒子の含有量（重量％）を示す。）
【００８８】
なお、各粒子の含有量、鉄及び黄燐の含有量は、スラリーの一部を固液分離し、乾燥した赤燐粉末中に含まれる含有量を示す。また、粒度特性、鉄と黄燐の含有量は前記と同様な方法で求めた。
【００８９】
また、用いた液体サイクロンは、図１に示す構造の液体サイクロンで、下記の寸法の二液分離型のものを２機用いた。
・円筒部内径（ａ）：５６．５ｍｍ
・円錐部分の傾斜角（ｄ）：２１．２度
・上部円筒部分の長さ（ｂ）：５８ｍｍ
・下部円錐部分の長さ（ｃ）：１３５ｍｍ
・上流の抜き出し部分の管径（ｆ）：１１．８ｍｍ
・下流の抜き出し部分の管径（ｅ）：５ｍｍ
また、操作条件は以下のとおりである。
・送入圧；０．０５ＭＰａ
・流量分配比（上流／下流）；２／１
【００９０】
比較例１
実施例１と同様に第一工程を実施した後、得られた赤燐粒子を含有するスラリー５００ｋｇを別に用意した攪拌機付きの円筒型（容量２０００Ｌ）タンクに入れ、３０分攪拌、攪拌を止め３０分静置、円筒型タンク内のスラリーの上部の２／３を抜き取り、抜き取り分の水を補給する操作を６回繰り返してタンクデカンテーション法により微粒子カット（カット点５μｍ）を実施した。なお、６回の排出で抜き取られたスラリー量は合計で４００ｋｇであった。
【００９１】
また、６回抜き取り後のタンク内に存在する赤燐粒子を含有するスラリーの一部を固液分離し、乾燥した赤燐粉末を得、この乾燥赤燐粉末中に含まれる各粒子の含有量、鉄及び黄燐の含有量を実施例１と同様に測定した。その結果及び処理に要した時間及び５μｍ未満の赤燐粒子の除去率を表３に示す。
【００９２】
なお、除去率は、下記計算式（２）に求めた。
【００９３】
【数２】

【００９４】
（式中のα₁ はタンクデカンテーション法を実施する前の赤燐粒子全体量に占める５μｍ未満の粒子の含有量（重量％）、β₁ はタンクデカンテーション法後の赤燐粒子全体量に占める５μｍ未満の粒子の含有量（重量％）を示す。）
【００９５】
比較例２
実施例１と同様に第一工程を実施した後、得られた赤燐粒子を含有するスラリー５００ｋｇを別に用意した容量５００Ｌの溢簸実験槽（向流接触式洗浄槽、上部：円筒型、下部：逆円錐型）に仕込み、下部より定量ポンプで水を送入して微粒子のみをオーバーフローさせる方法（水簸法）で微粒子をカットした。この時オーバーフローして回収したスラリーは２０００ｋｇであった。
【００９６】
また、水簸法後の溢簸実験槽中の赤燐粒子を含有するスラリーの一部を固液分離し、乾燥した赤燐粉末を得た。この乾燥赤燐粉末中に含まれる各粒子の含有量、鉄及び黄燐の含有量を実施例１と同様に測定した。その結果及び処理に要した時間及び５μｍ未満の赤燐粒子の除去率を表３に示す。
【００９７】
なお、除去率は、下記計算式（３）に求めた。
【００９８】
【数３】

【００９９】
（式中のα₂ は水簸法を実施する前の赤燐粒子全体量に占める５μｍ未満の粒子の含有量（重量％）、β₂ は水簸法後の赤燐粒子全体量に占める５μｍ未満の粒子の含有量（重量％）を示す。）
【０１００】
【表３】

【０１０１】
表３の結果より、５μｍ未満の赤燐粒子の除去手段として、液体サイクロンを用いることにより５μｍ未満の赤燐粒子を短時間で且つ効率よく除去することができることが分かる。
【０１０２】
＜ホスフィンガス発生量の測定＞
実施例１及び比較例１〜２のスラリーから固液分離して乾燥して得た赤燐各０．５ｇをアルミナボードに採取し、試験管に入れ窒素ガス中で２５０℃、１時間加熱した。発生したＰＨ₃ 量をテドラーバックに捕集して検知機で測定した。その結果を表４に示す。
【０１０３】
＜リンのオキソ酸の溶出量の測定＞
実施例１及び比較例１〜２のスラリーから固液分離して乾燥して得た赤燐各８ｇを１００ｍｌのポリプロピレン製ビンに採取し、蒸留水８０ｍｌを加えて密栓する。送風定温乾燥機にて８０℃で２０時間加熱、抽出後、乾燥機より取り出し、１０分以内に常温まで冷却し、上澄み液をろ過した後、ろ液中の溶出ＰＯ₄ イオン、ＰＨＯ₃ イオン及びＰＨ₂ Ｏ₂ イオンの濃度をイオンクロマトグラフで測定した。その結果を表４に示した。
【０１０４】
【表４】

【０１０５】
表４の結果より、５μｍ未満の赤燐粒子を赤燐全体量の５重量％以下まで低減したものは、ホスフィン発生量とリンのオキソ酸の溶出量が低減されていることが分かる。
【０１０６】
実施例２及び比較例３〜４
実施例１及び比較例１〜２で得られた各赤燐粒子を含有するスラリーに水を加えて１０％スラリーとし、このスラリー７３５ｇに、３０％過酸化水素水溶液を０．７ｍｌ加えた。次いで、水酸化ナトリウム水溶液でｐＨを１０に調製し、８０℃で６時間保持した。次いで、硝酸を加え、ｐＨを１に調製した後、８０℃で４時間処理した後、ろ過し、スラリーのｐＨが８となるまで水で洗浄した。
【０１０７】
次いで、得られたスラリーから一部赤燐粒子を回収し、乾燥後、鉄と黄燐とを実施例１と同様な方法で測定した。その結果を表５に示す。また、実施例１と同様な方法でＰＨ₃ 発生量と溶出したリンのオキソ酸の量を測定した。その結果を表５に示す。
【０１０８】
【表５】

【０１０９】
表５の結果より、赤燐粒子を含有するスラリーを酸処理、アルカリ処理を施して鉄と黄燐の含有量を低減することにより、ホスフィン発生量とリンのオキソ酸の溶出量を低減させることができることが分かる。
【０１１０】
実施例３及び比較例５〜６
実施例２及び比較例３〜４で得られたスラリーに水を加えて１０％スラリーに調製し、このスラリー３００ｇにＡｌ₂ Ｏ₃ として８重量％の硫酸アルミニウム４８．９ｇを加えて、攪拌しながら２．９ｗｔ％アンモニア水でｐＨ８に調製し、８０℃で３時間熟成を行った。
【０１１１】
放冷を行った後、遠心ろ過機によりろ過して、反応液から被覆赤燐を回収した。この被覆赤燐を、再び水を加えてスラリーとした後、常法によりリパルプして、この被覆赤燐の１０％スラリーとした時の２５℃の電気伝導度が３０μｓ／ｃｍ以下になるまで洗浄した。洗浄した被覆赤燐を減圧下に１１０℃で６時間乾燥し安定化赤燐を得た。得られた安定化赤燐の諸物性を表６に示す。
【０１１２】
【表６】

【０１１３】
（注）表６中の電気伝導度は２５℃における安定化赤燐の１０％スラリーの値である。電気伝導度は、溶出イオンの測定用検液を使用して、電気伝導計により得られた値である。
【０１１４】
＜ホスフィンガス発生量の測定＞
実施例３及び比較例５〜６で得られた安定化赤燐各０．５ｇをアルミナボードに採取し、試験管に入れ窒素ガス中で２５０℃、１時間加熱した。発生したＰＨ₃ 量をテドラーバックに捕集して検知機で測定した。その結果を表７に示す。
【０１１５】
＜リンのオキソ酸の溶出量の測定＞
実施例３及び比較例５〜６で得られた各安定化赤燐８ｇを１００ｍｌのポリプロピレン製ビンに採取し、蒸留水８０ｍｌを加えて密栓する。送風定温乾燥機にて８０℃で２０時間加熱、抽出後、乾燥機より取り出し、１０分以内に常温まで冷却し、上澄み液をろ過した後、ろ液中の溶出ＰＯ₄ イオン、ＰＨＯ₃ イオン及びＰＨ₂ Ｏ₂ イオンの濃度をイオンクロマトグラフで測定した。その結果を表７に示した。
【０１１６】
【表７】

【０１１７】
表７の結果より、本発明の製造方法で、ホスフィン発生量とリンのオキソ酸の溶出量が比較例のものと比べて低減されていることが分かる。
【０１１８】
実施例４
実施例４では、図３の実験装置を用いて実験を行った。この実験装置は、粗粒の赤燐粒子を含有するスラリーを貯蔵した容器１、湿式粉砕機のタワーミル７、ふるい目の開きの寸法が７５μｍの篩８、該篩８を通過したスラリーを一時的に貯蔵するための容器３、２機の液体サイクロン４−１及び４−２、液体サイクロン４−２の上部から排出された溶液を貯蔵するための上部容器５、ふるい目の開きの寸法が４５μｍの篩９を通過したスラリーを貯蔵するための下部容器６とを備える。
【０１１９】
前記タワーミル７で粉砕された粉砕物は溢流により、篩８に送られ、粒径７５μｍより大きな粒子は再びタワーミルに送られる。一方、この篩８を通過した粒子は、一時的に貯蔵するための容器３へ貯蔵される。また、液体サイクロン４−２の下部から排出されるスラリーは、篩９を通って、下部容器６に貯蔵される。
【０１２０】
（第一工程）
上記の粗粒の赤燐３３００ｋｇ（３．３ｔ）を水１００００Ｌに分散させたスラリーを調整し、これに硝酸を加えてｐＨ３．５に調製し容器１に貯蔵した。
次いで、このスラリーをタワーミル装置（日本タワーミル社製 形式ＶＷ−１５）７に導入し、湿式粉砕処理を行った。篩８を通過し、容器３に貯蔵された赤燐粒子を含有するスラリーの諸物性を表８に示す。なお、各粒子の含有量、鉄及び黄燐の含有量は、スラリーの一部を固液分離し、乾燥した赤燐粉末中に含まれる含有量を示す。なお、粒度特性、鉄及び黄燐の含有量を実施例１と同様な方法で測定した。
【０１２１】
また、タワーミル装置の操作条件は以下のとおりで行った。
・サイズ；高さ４．８ｍ×長さ３．６ｍ×幅２．８ｍ
・回転数；６０ｒｐｍ
・粉砕媒体；２．５ｃｍ径のアルミナボール
【０１２２】
【表８】

【０１２３】
（第二工程）
第一工程後のスラリー３００ｋｇに水を加えてスラリーの比重を１．０４に調製した後、これを液体サイクロン（三条鉄工社製）４−１及び４−２に供給した。液体サイクロンのボトム部から排出され、ふるい目の開き４５μｍの篩９を通過し、下部容器６に貯蔵されたスラリーの諸物性及び処理に要した時間を表９に示す。
【０１２４】
なお、各粒子の含有量、鉄及び黄燐の含有量は、スラリーの一部を固液分離し、乾燥した赤燐粉末中に含まれる含有量を示す。なお、粒度特性、鉄及び黄燐の含有量を実施例１と同様な方法で測定した。
【０１２５】
また、用いた液体サイクロンは、図１に示す構造の液体サイクロンで、下記の寸法の二液分離型のものを２機用いた。
・円筒部内径（ａ）：５６．５ｍｍ
・円錐部分の傾斜角（ｄ）：２１．２度
・上部円筒部分の長さ（ｂ）：５８ｍｍ
・下部円錐部分の長さ（ｃ）：１３５ｍｍ
・上流の抜き出し部分の管径（ｆ）：１１．８ｍｍ
・下流の抜き出し部分の管径（ｅ）：５ｍｍ
また、操作条件は以下のとおりである。
・送入圧；０．０５ＭＰａ
・流量分配比（上流／下流）；２／１
【０１２６】
【表９】

【０１２７】
次いで、上記で得られた赤燐粒子を含有するスラリーに水を加えて１０％スラリーとし、このスラリー７３５ｇに、３０％過酸化水素水溶液を０．７ｍｌ加えた。次いで、水酸化ナトリウム水溶液でｐＨを１０に調製し、８０℃で６時間保持した。次いで、硝酸を加え、ｐＨを１に調製した後、８０℃で４時間処理した後、ろ過し、１０％スラリーのｐＨが８となるまで水で洗浄した。スラリーの一部を固液分離し、実施例１と同様の方法で鉄と黄燐の含有量を測定したところ、乾燥した赤燐粉末中に含まれる鉄の含有量は０．０１重量％で、黄燐の含有量は０．００２重量％であった。
【０１２８】
次いで、洗浄後の赤燐を再び１０％スラリーとし、このスラリー３００ｇにＡｌ₂ Ｏ₃ として８重量％を含有する硫酸アルミニウム１．２ｇを加えて、攪拌しながら２．９％アンモニア水でｐＨ８に調製し、８０℃で３時間熟成を行った。
【０１２９】
放冷を行った後、常法によりろ過して反応液からこの被覆赤燐を回収し、再び水を加えてスラリーとした後、常法によりリパルプして、この被覆赤燐の１０％スラリーとした時の電気伝導度が１０００μｓ／ｃｍ以下になるまで洗浄を行った。
【０１３０】
次いで、この洗浄後の赤燐を再び１０％スラリーとし、２９ｗｔ％アンモニア水でｐＨ１０として、フェノール樹脂（大日本インキ社製、初期縮合物、フェノライトＴＤ２３８８；固形分２５％）を６ｇ加えた。
次いで、塩酸を用いてｐＨを６．５に調製し、次に９０℃で１時間硬化反応を行った。
【０１３１】
放冷した後、十分にスラリーをろ過、洗浄し、ろ過ケーキは減圧下に乾燥した後、１４０℃で１時間硬化処理を行い、放冷後１００メッシュの篩を通過させて安定化赤燐試料を得た。得られた安定化赤燐の諸物性を表１０に示す。また、実施例３と同様な方法で、ホスフィンガスの発生量とリンのオキソ酸の溶出量を測定した。その結果を表１０に示す。
【０１３２】
【表１０】

【０１３３】
（注）表中の電気伝導度は２５℃における安定化赤燐の１０％スラリーの値である。
【０１３４】
実施例５
実施例５は、図３の実験装置を用い、スラリーの製造を５回行い、品質安定性を評価した。
【０１３５】
（第一〜第二工程）
上記の粗粒の赤燐３３００ｋｇ（３．３ｔ）を水１００００Ｌに分散させたスラリーを調整し、これに硝酸を加えてｐＨ３．５に調製し、図３中の容器１に貯蔵した。
【０１３６】
次いで、このスラリーをタワーミル装置（日本タワーミル社製 形式ＶＷ−１５）７に導入し、湿式粉砕処理を行い、次いで、篩８を通過し、容器３に貯蔵された赤燐粒子を含有するスラリーに水を加えて比重を１．０４としたものを液体サイクロン（三条鉄工社製）４−１及び４−２に供給し、液体サイクロンのボトム部から排出され、篩９を通過したスラリーを下部容器６に貯蔵した。これにより第１回目のスラリーを得た。
【０１３７】
第２回目のスラリーは、第１回目のスラリーと同じように、上記の粗粒の赤燐３３００ｋｇを水１００００Ｌに分散させたスラリーを用いて、第１回目と同様に第一工程から第二工程の操作を行い、第２回目のスラリーを得た。
同様に、上記の第一工程から第二工程の操作を合計で５回行い下部容器６中に貯蔵された各スラリー中に含まれる赤燐粒子の粒度特性を実施例１と同様に測定した。その結果を表１１に示す。
また、第２工程の処理に要した時間を表１１に合わせて併記した。
【０１３８】
また、タワーミル装置の操作条件は下記のとおりである。
・サイズ；高さ４．８ｍ×長さ３．６ｍ×幅２．８ｍ
・回転数；６０ｒｐｍ
・粉砕媒体；２．５ｃｍ径のアルミナボール
【０１３９】
また、用いた液体サイクロンは、図１に示す構造の液体サイクロンで、下記の寸法の二液分離型のものを２機用いた。
・円筒部内径（ａ）：５６．５ｍｍ
・円錐部分の傾斜角（ｄ）：２１．２度
・上部円筒部分の長さ（ｂ）：５８ｍｍ
・下部円錐部分の長さ（ｃ）：１３５ｍｍ
・上流の抜き出し部分の管径（ｆ）：１１．８ｍｍ
・下流の抜き出し部分の管径（ｅ）：５ｍｍ
また、液体サイクロンの操作条件は以下のとおりである。
【０１４０】
・送入圧；０．０５ＭＰａ
・分配比率（上流／下流）；２／１
【０１４１】
【表１１】

【０１４２】
表１１の結果より、本発明の赤燐粒子を含有するスラリーの製造方法は、安定した品質のものを短時間で製造することができることが分かる。
【０１４３】
【発明の効果】
上記したとおり、本発明の赤燐粒子を含有するスラリーの製造方法によれば、工業的に有利な方法で、ホスフィンガスの発生、更にはリンのオキソ酸の溶出が少ない赤燐粒子を含有するスラリーを短時間で、且つ安定した品質で得ることができる。
【０１４４】
また、本発明の安定化赤燐の製造方法によれば、上記の赤燐粒子を含有するスラリーの製造方法により得られた赤燐粒子を製造原料として用いて、ホスフィンガスの発生量及びリンのオキソ酸の溶出量が効果的に抑制された安定化赤燐を得ることができる。
【図面の簡単な説明】
【図１】本発明に使用する液体サイクロンの代表的な構造を示す概略図である。
【図２】本発明の実施例１の第一工程と第二工程で用いた実験装置を示す概略図である。
【図３】本発明の実施例４及び実施例５の第一工程と第二工程で用いた実験装置を示す概略図である。
【符号の説明】
ａ 液体サイクロンの円筒部内径
ｂ 液体サイクロンの上部円筒部分の長さ
ｃ 液体サイクロンの下部円錐部分の長さ
ｄ 液体サイクロンの円錐部分の傾斜角
ｅ 液体サイクロンの下流抜き出し部分の管径
ｆ 液体サイクロンの上流抜き出し部分の管径
Ｐ ポンプ
１ 容器
２ ビーズミル
３ 容器
４−１，４−２ 液体サイクロン
５ 上部容器
６ 下部容器
７ タワーミル
８ ふるい目の開き寸法７５μｍの篩
９ ふるい目の開き寸法４５μｍの篩[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a slurry containing red phosphorus particles used as a raw material for producing a red phosphorus flame retardant capable of suppressing generation of phosphine gas and further elution of oxo acid of phosphorus, and phosphine gas using the same The present invention also relates to a method for producing stabilized red phosphorus in which generation of phosphine and elution of phosphorus oxoacids are suppressed.
[0002]
[Prior art]
Red phosphorus flame retardants are effective flame retardants as non-halogen flame retardants. However, there is a problem that a small amount of phosphine gas is generated due to the reaction between red phosphorus and moisture in the air, and phosphine oxo from the surface of red phosphorus. There is a problem that the acid is eluted.
[0003]
Conventionally, red phosphorus is produced by converting yellow phosphorus to red phosphorus by heating, so-called thermal conversion reaction.
The thermal conversion reaction proceeds by the formation of small red phosphorus nuclei and the growth and bonding of the nuclei, but as the conversion rate increases, formation of aggregate particles by interparticle bonding is promoted, resulting in formation. The red phosphorus particles rapidly become coarse and eventually solidify into massive red phosphorus.
[0004]
Usually, the consolidated massive red phosphorus is a coarse particle group, so when this is used as a raw material for the red phosphorus flame retardant, the massive red phosphorus is pulverized and fine particles are separated by a water tank method or the like. Removed and adjusted to the desired particle size characteristics have been used.
[0005]
However, when removing fine particles from red phosphorus by the elutriation method, etc., in order to increase the removal accuracy, it takes a long time for the treatment and requires a huge apparatus, and the particles under mild conditions. Since the difference in sedimentation between the large and small particles is used, the continuous classification process using this elutriation method makes it difficult to manage the operating conditions, and the red color obtained in this way. The slurry containing phosphorus particles has a drawback that it is difficult to obtain a stable quality from which fine particles have been removed.
[0006]
For example, red phosphorus particles having a particle size of 1 μm or less contained as fine particles are technically difficult to coat and stabilize the surface of the red phosphorus particles, It is known that when the content increases, the amount of phosphine gas generated and the amount of phosphorus oxoacid eluted tend to increase (see, for example, Patent Documents 1 to 4).
[0007]
[Patent Document 1]
JP-A-63-134507 (first page, third page)
[Patent Document 2]
JP-A-63-230510 (first page, third page)
[Patent Document 3]
Japanese Patent Application Laid-Open No. 64-24008 (first page, second page)
[Patent Document 4]
JP-A-1-286909 (2nd and 3rd pages)
[0008]
[Problems to be solved by the invention]
While searching for the cause of the generation of phosphine gas and the elution of phosphorus oxoacid, the present inventors have found that the presence of red phosphorus particles having a particle size of 1 μm or less is less than 5 μm. When the content of these fine particles is reduced, generation of phosphine gas and elution of oxo acid of phosphorus are suppressed, and removal of these fine particles is performed using a liquid cyclone. The present invention has been found that it can be performed accurately and efficiently in a short time compared to the prior art, and that when a liquid cyclone is used, a stable quality with fine particles removed can be obtained even if the classification process is continuously performed. It came to be completed.
[0009]
That is, the object of the present invention is to be industrially advantageous in that it can effectively suppress generation of phosphine gas and elution of oxo acid of phosphorus when used as a raw material for producing a red phosphorus flame retardant. And a method for producing a stabilized red phosphorus that suppresses generation of phosphine gas and further elution of oxo acid of phosphorus using the slurry. It is to provide.
[0010]
[Means for Solving the Problems]
  The first object of the present invention is achieved by a method for producing a slurry containing the following red phosphorus particles.
  According to the method for producing a slurry containing red phosphorus particles of the present invention, a slurry containing raw material red phosphorus particles containing iron and yellow phosphorus as impurities is wet-pulverized, and a red particle having a particle size of 45 μm or less contained in the slurry. A first step of preparing a slurry in which the content of phosphorus particles is 50% by weight or more of the total amount of red phosphorus particles, and the slurry prepared in the first step is treated with a hydrocyclone and contained in the slurry. The second step of preparing a slurry in which the content of red phosphorus particles having a particle size of less than 5 μm is 5% by weight or less of the total amount of red phosphorus particles and having an average particle size of 10 to 40 μm, before the first step, After the process, at any time after the second process, the slurry containing red phosphorus particlesAcid and alkaliAdding to treat the red phosphorus particles,Included in red phosphorus particlesImpurityThe iron content is 0.1 wt% or less and the yellow phosphorus content is 0.005 wt% or less.It is a manufacturing method of the slurry containing the red phosphorus particle | grains characterized by including the process to reduce.
[0011]
In the second step, it is preferable to prepare a slurry in which the content of particles having a particle size of less than 5 μm is 5% by weight or less of the total amount of red phosphorus particles.
The second object of the present invention is achieved by the following method for producing stabilized red phosphorus. The method for producing stabilized red phosphorus according to the present invention includes at least one selected from Zn, Al, Mg, Ti, Si, Co, Zr, and Sn in a slurry containing red phosphorus particles produced by the above method. And a step of preparing an aqueous suspension by adding a water-soluble metal salt and a step of adding an alkali to the aqueous suspension to precipitate the metal salt on the surface of red phosphorus particles. This is a method for producing red phosphorus.
[0012]
The method for producing stabilized red phosphorus according to the present invention comprises a step of solid-liquid separation of a slurry containing red phosphorus particles produced by the above method to obtain red phosphorus particles; Adding at least one water-soluble metal salt selected from Zn, Al, Mg, Ti, Si, Co, Zr, and Sn to the step of preparing the slurry to be contained, and the slurry containing the red phosphorus particles; A method for producing stabilized red phosphorus, comprising a step of preparing an aqueous suspension and a step of adding an alkali to the aqueous suspension to precipitate a metal salt on the surface of red phosphorus particles.
[0013]
The method for producing stabilized red phosphorus according to the present invention comprises adding a raw material for synthesizing a thermosetting resin or an initial condensate thereof to a slurry containing the stabilized red phosphorus produced by the above method, and performing a polymerization reaction. This is a method for producing stabilized red phosphorus.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, the present invention will be described in detail.
  According to the method for producing a slurry containing red phosphorus particles of the present invention, a slurry containing raw material red phosphorus particles containing iron and yellow phosphorus as impurities is wet-pulverized, and a red particle having a particle size of 45 μm or less contained in the slurry. A first step of preparing a slurry in which the content of phosphorus particles is 50% by weight or more of the total amount of red phosphorus particles, and the slurry prepared in the first step is treated with a hydrocyclone and contained in the slurry. The second step of preparing a slurry in which the content of red phosphorus particles having a particle size of less than 5 μm is 5% by weight or less of the total amount of red phosphorus particles and having an average particle size of 10 to 40 μm, before the first step, After the process, at any time after the second process, the slurry containing red phosphorus particlesAcid and alkaliAdding to treat the red phosphorus particles,Included in red phosphorus particlesImpurityThe iron content is 0.1 wt% or less and the yellow phosphorus content is 0.005 wt% or less.Including a step of reducing.
[0015]
In the first step of the present invention, a slurry containing raw material red phosphorus particles is supplied to a wet pulverizer and subjected to a wet pulverization treatment, and the content of red phosphorus particles having a particle size of 45 μm or less contained in the slurry is 50 wt. % Or more, preferably 60% by weight or more.
[0016]
In this first step, by adjusting the particle size characteristics of the red phosphorus particles in the slurry to be in the above range, the target red phosphorus particles having an average particle diameter of 10 to 40 μm can be obtained in high yield. .
[0017]
The red phosphorus particles used as raw materials are coarse red phosphorus particles, for example, massive red phosphorus obtained by converting yellow phosphorus into red phosphorus by heat, and the content of particles having a particle size exceeding 75 μm is the total amount of red phosphorus particles. The content of particles having a particle size of 10% by weight or more and a particle size of 45 μm or less is less than 50% by weight of the total amount of red phosphorus particles, and other physical properties are not particularly limited. The content of Fe that is a decomposition catalyst of red phosphorus contained in 0.1% by weight or less, preferably 0.05% by weight or less, is chemically unstable and ignitable, and the phosphorus oxoacid The content of yellow phosphorus, which is one factor for elution and generation of phosphine gas, is 0.005% by weight or less, preferably 0.002% by weight or less. By applying alkali treatment, these impurities , And further generation of phosphine gas and elution of phosphorus oxoacid can be reduced.
[0018]
In the first step, first, a slurry containing 5 to 60 parts by weight, preferably 10 to 55 parts by weight of the above-described coarse red phosphorus particles in 100 parts by weight of water is prepared. Specifically, the slurry is prepared by adding a predetermined amount of water to coarse red phosphorus particles.
[0019]
Next, the slurry containing the coarse red phosphorus particles is supplied to a wet pulverizer.
Examples of wet pulverizers that can be used include wet pulverizers such as a ball mill and a bead mill. Among these, the use of a tower mill as the ball mill is preferable because generation of fine particles due to pulverization can be suppressed as much as possible, so that classification operation can be efficiently performed in a liquid cyclone in the next step.
[0020]
In the present invention, the wet pulverization treatment in the tower mill can be efficiently pulverized using the difference in sedimentation rate between the large and small particles when carried out in the presence of an acid, and the particle size is less than 5 μm. In the resulting slurry, the content of particles having an unnecessary particle size of 100 μm or more, preferably 75 μm or more, and the content of particles having a particle size of less than 5 μm can be reduced. .
[0021]
In this case, the acid that can be used is not particularly limited, and examples thereof include nitric acid, sulfuric acid, hydrochloric acid, sulfurous acid, and the like, and these acids can be used alone or in combination of two or more. Of these, nitric acid is particularly preferred because it can be used without corrosion of the apparatus.
Usually, it is desirable that the acid is added to the slurry containing coarse red phosphorus particles so that the adjusted slurry has a pH of 4 or less.
[0022]
This first step may be performed any number of times until the above-mentioned particle size is obtained, and two or more wet pulverizers, or a combination of a wet pulverizer and a classification operation such as a sieve and a water tank. Then, a slurry containing red phosphorus particles having a particle size characteristic in the above range may be prepared.
[0023]
In the second step, the slurry after the first step is supplied to a hydrocyclone and processed to prepare a slurry in which the content of particles having a particle size of less than 5 μm contained in the slurry is reduced.
[0024]
In the present invention, the reason for reducing the content of particles having a particle size of less than 5 μm is that, as described above, the red phosphorus particles having a particle size of less than 5 μm cause the generation of phosphine gas. By reducing the content, generation of phosphine gas and elution of phosphorus oxo acid can be suppressed. In this second step, the content of red phosphorus particles having a particle size of less than 5 μm is adjusted to 5% by weight or less, preferably 3% by weight or less of the total amount of red phosphorus particles. It is particularly preferable for suppressing elution.
[0025]
The liquid cyclone that can be used is a two-part separation type in which fine particles are discharged from the top (upper part) of the device and coarse particles are discharged from the bottom (bottom) of the device, or finer powder that is finer than fine particles. A three-component separation type in which the fine particles are discharged from the middle part (intermediate part) of the apparatus and the coarse particles are discharged from the bottom part of the apparatus can be used.
[0026]
The liquid cyclone is preferably made of ceramic, silicon nitride, or urethane resin in order to ensure corrosion resistance and wear resistance. In the present invention, one or more liquid cyclones may be operated in parallel. For example, when a plurality of liquid cyclones are operated in parallel, the processing capacity increases, thereby enabling mass production and improving productivity. Can do.
[0027]
FIG. 1 is a schematic view showing a typical structure of a hydrocyclone used in the present invention. In the figure, a is the cylindrical inner diameter of the hydrocyclone, b is the length of the upper cylindrical portion, c is the length of the lower conical portion, d is the inclination angle of the conical portion, e is the tube diameter of the downstream extraction portion, and f is the upstream The tube diameter of the extracted part is shown. X is a stock solution, Y is downstream, and Z is upstream.
[0028]
The mechanism for separating particles by the hydrocyclone shown in FIG. 1 can efficiently remove particles having a particle size of less than 5 μm from the slurry by utilizing the difference in centrifugal sedimentation speed between the particles.
[0029]
Classification efficiency by hydrocyclone changes depending on conditions such as slurry feeding pressure (feeding speed) to liquid cyclone, specific gravity of slurry to be supplied (slurry concentration), and distribution ratio of upstream and downstream flow rate in liquid cyclone. These operating conditions include the relationship between the inner diameter a of the upper cylindrical portion of the hydrocyclone to be used, the inclination angle d of the conical portion, the length b of the upper cylindrical portion, and the length c of the lower conical portion, and the upstream and downstream sides. It varies depending on the tube diameters f and e of the extracted portion.
[0030]
For example, as a hydrocyclone, the cylindrical portion inner diameter a is 56.5 ± 0.5 mm, the inclination angle d of the conical portion is 21.2 degrees, the length b of the upper cylindrical portion is 58 ± 0.5 mm, and the length of the lower conical portion. Red phosphorus particles using a two-liquid separation type in which c is 135 ± 5 mm, the tube diameter f of the upstream extraction portion is 11.8 ± 0.5 mm, and the tube diameter e of the downstream extraction portion is 5 ± 0.5 mm In the case where a slurry having a specific gravity of 1.02 to 1.08 is supplied to the liquid cyclone, the slurry is supplied to the liquid cyclone at a feed pressure of 0.025 to 0.1 MPa, preferably 0.8. The flow rate distribution ratio (Z / Y) of the flow rate of the upstream Z / downstream Y is 1.5 to 2.5 / 1, preferably 1.8 to 2.2 / 1, and the bottom portion ( By collecting the slurry from symbol e) in FIG. Those having a diameter of less than 5 μm can be efficiently removed.
[0031]
In addition, it is particularly preferable to supply the slurry to the hydrocyclone because it is possible to obtain a stable quality by operating the slurry so that the specific gravity (slurry concentration) of the slurry and the supply pressure of the slurry are always constant.
[0032]
The slurry containing red phosphorus particles thus obtained has an average particle size of red phosphorus particles contained in the slurry of 10 to 40 μm, preferably 20 to 35 μm, and the content of particles having a particle size of less than 5 μm is red phosphorus particles. A slurry having a total amount of 5% by weight or less, preferably 3% by weight or less can be obtained. Further, in addition to the above particle size characteristics, if the content of particles having a particle size of 1 μm or less is 0.5% by weight or less, preferably 0.1% by weight or less of the total amount of red phosphorus particles, generation of phosphine gas or phosphorus oxoacid This is particularly preferable since elution of the can be further reduced.
[0033]
The concentration of the slurry containing red phosphorus particles after completion of the second step is such that the content of the red phosphorus particles contained in the slurry is 100 parts by weight of water and the particle size-adjusted red phosphorus particles are 3 It is desirable to contain -45 parts by weight, preferably 7-42 parts by weight.
[0034]
In the method for producing a slurry containing red phosphorus particles of the present invention, for example, the particle size of 45 μm contained in the slurry using a sieve having a sieve opening of 45 μm before or after the second step. Is sufficiently removed until the content of particles exceeding 5% by weight or less, preferably 3% by weight or less of the total amount of red phosphorus particles is used by controlling the maximum particle size in the application, for example, electric wires, cables, It can be suitably used as a raw material for producing a red phosphorus flame retardant such as a sealing material. In this case, it is particularly preferable to control the maximum particle size described above by passing the slurry treated with the hydrocyclone as it is through the sieve as described above, because a large amount can be efficiently processed in a short time.
[0035]
In the method for producing a slurry containing red phosphorus particles of the present invention, the content of iron contained in the red phosphorus particles is 0.1% by weight or more and / or the content of yellow phosphorus is 0.005% by weight or more. In some cases, it is preferable to add an acid or alkali to the slurry and to perform acid or / and alkali treatment.
[0036]
That is, by treating the red phosphorus particles with an alkali, it is possible to remove yellow phosphorus, which is chemically unstable and ignited, and which causes one of elution of phosphoric acid and generation of phosphine gas, By treating with an acid, impurities such as iron, which are oxidation catalysts for red phosphorus, can be effectively removed.
[0037]
Specifically, the alkali treatment is such that the slurry concentration is adjusted to 20 to 40 parts by weight, preferably 25 to 35 parts by weight of red phosphorus particles with respect to 100 parts by weight of water, and then the pH of the slurry is 10 or more. The alkaline agent is preferably added so as to be 10.5 or more, and the mixture is processed at a temperature of 40 to 95 ° C., preferably 75 to 90 ° C. for 2 hours or more, preferably 4 hours or more with stirring.
[0038]
The alkali agent that can be used is not particularly limited, and examples thereof include ammonia gas, ammonia water, caustic soda, caustic potash, NaHCO 3._Three , Na₂ CO_Three , K₂ CO_Three , KHCO_Three An inorganic alkali such as ethanolamine or an organic alkali such as ethanolamine can be used, and these can be used alone or in combination.
[0039]
In the present invention, the alkali treatment is, for example, phosphine generated at the time of cleaning when an oxidizing agent such as hydrogen peroxide, perchloric acid, potassium permanganate, sodium permanganate or ozone is present in the system. It is preferable because the gas can be oxidized to phosphorus oxo acid at any time and work can be safely performed. In this case, the amount of the oxidizing agent is not particularly limited, but is 100 parts by weight of the red phosphorus particles. In many cases, 0.001 to 0.5 parts by weight is sufficient.
[0040]
On the other hand, in the specific acid treatment operation, the slurry concentration is adjusted so that the amount of red phosphorus particles is 20 to 40 parts by weight, preferably 25 to 35 parts by weight with respect to 100 parts by weight of water. The acid is added so as to be 4 or less, preferably 2 or less, and the mixture is stirred at a temperature of 40 to 95 ° C., preferably 75 to 90 ° C. for 1 hour or more, preferably 4 hours or more.
[0041]
Although it does not restrict | limit especially as an acid which can be used, For example, nitric acid, a sulfuric acid, hydrochloric acid, sulfurous acid etc. 1 type or 2 types or more are mentioned, In this, nitric acid has high removal efficiency of iron, This is particularly preferable because there is no corrosion of the apparatus.
[0042]
In the method for producing a slurry containing red phosphorus particles of the present invention, the alkali treatment and the acid treatment can be used in appropriate combination.
The acid treatment or alkali treatment may be performed before the first step, after the first step, or after the second step.
[0043]
In addition to the above particle size characteristics, the slurry containing red phosphorus particles subjected to acid or alkali treatment thus obtained has an iron content of 0.1 wt% or less, preferably 0.05. Less than wt%, yellow phosphorus content is 0.005 wt% or less, preferably 0.002 wt% or less. By using the red phosphorus particles as a raw material for producing red phosphorus flame retardants, only the generation of phosphine gas In addition, it is possible to further effectively suppress the elution of phosphorus oxoacids eluted from red phosphorus.
[0044]
In addition, the slurry containing the red phosphorus particles of the present invention can be used as a product as it is. For example, after the completion of the second step, the red phosphorus particles are recovered by solid-liquid separation by a conventional method. Therefore, it can be stored in a wet state or a dry product.
[0045]
Next, the manufacturing method of the stabilized red phosphorus of this invention is demonstrated.
(Method for producing stabilized red phosphorus)
Stabilized red phosphorus obtained by the production method of the present invention is a slurry containing red phosphorus particles obtained by the production method described above, or red phosphorus particles obtained by solid-liquid separation from the slurry as a raw material, The surface of the red phosphorus particles is coated with a stabilized red phosphorus (hereinafter referred to as “first stabilized red phosphorus”), or the surface of the red phosphorus particles is coated with an inorganic material. This is double-coated red phosphorus (hereinafter referred to as “second stabilized red phosphorus”) in which the surface of the red phosphorus particles coated with an inorganic substance is further coated with a thermosetting resin.
[0046]
The method for producing the first stabilized red phosphorus is (a) using a slurry containing red phosphorus particles obtained by the above production method, or (b) wet obtained by solid-liquid separation of the slurry. Using the red phosphorus particles in a state or dry red phosphorus particles obtained by drying them, a slurry containing red phosphorus particles prepared to a desired concentration is prepared, or consists of either (a) or (b) above Step (A1), and then adding at least one water-soluble metal salt selected from Zn, Al, Mg, Ti, Si, Co, Zr, and Sn and an alkali agent to the slurry containing the red phosphorus particles Then, a hydroxide or oxide of these metals is precipitated on the surface of the red phosphorus particles (A2), and then the red phosphorus coated with the obtained inorganic substance is washed with water (A3).
[0047]
In the step (A1), the slurry containing the red phosphorus particles (a) is a slurry containing 5 to 100 parts by weight, preferably 10 to 80 parts by weight of red phosphorus particles with respect to 100 parts by weight of water. is there. The slurry containing red phosphorus particles in (b) is 5 to 100 parts by weight, preferably 10 to 80 parts by weight of red phosphorus particles in wet state or dry red phosphorus particles with respect to 100 parts by weight of water. The slurry concentration is adjusted to include
[0048]
Specifically, in the step (A2), at least one water-soluble metal salt selected from Zn, Al, Mg, Ti, Si, Co, Zr, and Sn is added to the slurry prepared in the step (A1). In addition, 0.05 to 12 parts by weight, preferably 0.1 to 10 parts by weight, are added as metal based on 100 parts by weight of red phosphorus particles, and ammonia gas, aqueous ammonia, caustic soda, caustic potash, NaHCO 3 are added._Three , Na₂ CO_Three , K₂ CO_Three , KHCO_Three At least one alkali selected from an inorganic alkali agent such as ethanolamine or an organic alkali such as ethanolamine, and the pH of the slurry is adjusted to 6 to 10, and the temperature is 40 to 95 ° C, preferably 75 to 90 ° C. The reaction can be performed by aging and precipitation of the metal hydroxide or oxide on the surface of the red phosphorus particles.
[0049]
When coating the red phosphorus particles with zinc hydroxide, it is preferable to keep the pH at 6.5 or higher at all times.
[0050]
The step (A3) is a step of washing the red phosphorus coated with the inorganic substance after the step (A2) with water. In the present invention, it is preferable to use a product obtained by reducing the electrical conductivity at 25 ° C. to a desired value when this washing is a 10% slurry of the first stabilized red phosphorus. By setting the degree to 1000 μs / cm or less, it can be used as a flame retardant for general-purpose products such as building materials, paints, and household products. Preferably, the electrical conductivity is 300 μs / cm or less, for example, It can be used as a flame retardant for electric wires, cables, phenolic resin molding materials, plywood adhesives, foamed polyethylene and the like.
[0051]
A method for performing this cleaning is not particularly limited, but it is particularly preferable to perform the cleaning by means such as repulp because of high cleaning efficiency.
After completion of washing, the product is dried in an inert gas atmosphere.
[0052]
The first stabilized red phosphorus thus obtained preferably has a red phosphorus content of 80% by weight or more because it can impart excellent flame retardancy to the polymer material. If it is less than 80% by weight, it tends to agglomerate due to the coating component, and if it exceeds 98% by weight, the coating amount is small, so that it is likely to lack stability to suppress generation of phosphine gas and elution of phosphorus oxoacid. Therefore, the red phosphorus content is preferably 80 to 98% by weight.
[0053]
Further, as the particle size characteristics of the first stabilized red phosphorus, an average particle size of 10 to 40 μm, preferably 18 to 25 μm, is preferable because of excellent dispersibility in various polymer materials. The content of particles having a particle size of less than 5 μm is 5% by weight or less, preferably 3% by weight or less, more preferably the content of 1 μm in particle size is 0.5% by weight or less, preferably 0.1% by weight or less. It is preferable because generation of phosphine gas and elution of phosphorus oxo acid are further reduced. Further, in addition to the above particle size characteristics, the maximum particle size is required to be 5% by weight or less, preferably 3% by weight or less, and the content of particles exceeding 45 μm is, for example, as a red phosphorus flame retardant for electric wires, cables, etc. It can be used suitably.
[0054]
Next, in the method for producing the second stabilized red phosphorus, the step (B1) of preparing a slurry containing the first stabilized red phosphorus particles, and then the slurry containing the first stabilized red phosphorus particles Step (B2) of adding a thermosetting resin synthetic raw material or an initial condensate thereof to carry out a polymerization reaction, and then washing the resulting first stabilized red phosphorus coated with the thermosetting resin with water (B3) It has a process.
[0055]
The step (B1) is a step of preparing a slurry containing the first stabilized red phosphorus particles. Specifically, a slurry containing 5 to 30 parts by weight, preferably 10 to 20 parts by weight of the first stabilized red phosphorus is prepared with respect to 100 parts by weight of water.
In addition, in this (B1) process, you may use the reaction liquid after the said (A2) process as it is for the slurry containing a said 1st stabilization red phosphorus.
[0056]
Specifically, in the step (B2), for example, a phenol resin, a melamine resin, an epoxy resin, an unsaturated polyester resin, a phenol-formalin resin, a urea-formalin is added to the slurry prepared in the step (B1). A synthetic raw material of a thermosetting resin selected from a resin, a melamine-formalin resin or the like or an initial condensate thereof is added. For example, when a phenolic resin is used as the coating resin, an acid such as hydrochloric acid, nitric acid or sulfuric acid and, if desired, an alkali such as ammonia or sodium hydroxide are added to the slurry prepared in step (B1). 0.25 to 10 parts by weight, preferably 0.5 to 5 parts by weight of an initial condensate (as solid content), and optionally adding ammonium chloride as a buffering agent at 60 to 90 ° C. for 1 to 3 hours It can implement by performing a polymerization reaction, stirring.
[0057]
In the step (B2), when the stabilized red phosphorus coated with zinc hydroxide is used as the first stabilized red phosphorus, an alkali is appropriately added and the thermosetting resin is polymerized at a pH of 6.5 or higher. It is preferable to carry out the reaction.
[0058]
Further, in this step (B2), if desired, for example, ZnO or ZnCO having a particle size of 2 μm or less, preferably 0.2 to 1 μm._Three , Zn₂ SiO_Four , Al₂ O_Three , ZrO₂ TiO₂ And SnO₂ The polymerization reaction may be carried out by adding at least one metal compound selected from 0.25 to 20 parts by weight in the reaction system.
[0059]
The step (B3) is a step of washing the second stabilized red phosphorus coated with the thermosetting resin obtained in the step (B2) with water. In the present invention, this washing is preferably carried out until the electric conductivity at 25 ° C. when the 10% slurry of the second stabilized red phosphorus is reduced to a desired value. Usually, by setting the electrical conductivity to 1000 μs / cm or less, it can be used as a flame retardant for general-purpose products such as building materials, paints, and household products. It can be used as a flame retardant such as an electric wire, a cable, a phenol resin molding material, an adhesive for plywood, and foamed polyethylene.
[0060]
A method for performing this cleaning is not particularly limited, but it is particularly preferable to perform the cleaning by means such as repulp because of high cleaning efficiency.
After completion of washing, the product is dried in an inert gas atmosphere.
[0061]
The second stabilized red phosphorus thus obtained is more strongly coated with a thermosetting resin than the first stabilized red phosphorus, so that further generation of phosphine gas and elution of phosphorus oxoacids can be achieved. In addition, it is preferable that the red phosphorus content is 80% by weight or more because it is possible to impart excellent flame retardancy to the polymer material, while the red phosphorus content is 80% by weight. Less than 98% by weight, the coating amount is small, so that it is likely to lack stability to suppress the generation of phosphine gas and the elution of phosphorus oxoacids. The content is preferably 80 to 98% by weight. The content of particles having a particle size of less than 5 μm is 5% by weight or less, preferably 3% by weight or less, more preferably the content of 1 μm in particle size is 0.5% by weight or less, preferably 0.1% by weight or less. It is preferable because generation of phosphine gas and elution of phosphorus oxo acid are further reduced. Further, in addition to the above particle size characteristics, the maximum particle size is required to be 5% by weight or less, preferably 3% by weight or less, and the content of particles exceeding 45 μm is, for example, red phosphorus such as electric wires, cables and sealing materials. It can be suitably used as a system flame retardant.
[0062]
The stabilized red phosphorus obtained in the present invention can be suitably used as a red phosphorus flame retardant for various polymer materials, and the red phosphorus flame retardant is blended in a polymer material and is kneaded and molded. In the above, since generation of phosphine gas and elution of phosphorus oxo acid are suppressed, it is suitable as a flame retardant.
[0063]
The polymer material that can be used is not particularly limited. For example, epoxy resin, phenol resin, polyurethane resin, melamine resin, urea resin, aniline resin, furan resin, alkyd resin, xylene resin, unsaturated polyester resin, diaryl Curable resin such as phthalate resin, polyvinyl chloride, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate, polyphenylene oxide, polyphenylene ether, nylon 6, nylon 66, nylon 12, polyacetal, polyethylene, polypropylene, polybutadiene, polyacrylonitrile, polystyrene , Polymethyl methacrylate, polyethylene oxide, polytetramethylene oxide, thermoplastic polyurethane, phenoxy resin, polyamide, Rene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / Examples thereof include thermoplastic resins such as glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, polyester polyether elastomer, polytetrafluoroethylene, and modified products thereof. These resins may be homopolymers or copolymers, and may be a mixture of two or more.
[0064]
Here, the curable resin is chemically changed by the action of heat, catalyst, or ultraviolet rays to develop a crosslinked structure, has a three-dimensional network structure with increased molecular weight, and is cured to be semipermanent. A synthetic resin that is insoluble and infusible. The thermoplastic resin refers to a resin that exhibits fluidity by heating and can be shaped by this.
[0065]
The polymer material in the present invention may be rubber, for example, natural rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), polybutadiene rubber (BR). , Ethylene-propylene rubber (EPDM), chloroprene rubber (CR), polyisobutylene rubber, allyl rubber, hydrogenated acrylonitrile-butadiene rubber, polysulfide rubber, urethane rubber, chlorosulfonated rubber, silicone rubber and modified products thereof These may be two or more kinds of blend rubbers.
[0066]
The polymer material used in the present invention may be a blend of two or more selected from the curable resin, thermoplastic resin or rubber.
The blending ratio of the stabilized red phosphorus of the present invention to various polymer materials is 2 to 20 parts by weight, preferably 3 to 10 parts by weight as P with respect to 100 parts by weight of the polymer material.
[0067]
Moreover, the stabilized red phosphorus of the present invention can be used in combination with other flame retardants.
Examples of other flame retardants that can be used in combination include hydrated metal compounds, phosphorus flame retardants, and nitrogen-containing flame retardants.
[0068]
As a hydrated metal compound, M has a combustion suppressing action by an endothermic reaction._mO_n XH₂A compound represented by O (M is a metal, m, n is an integer of 1 or more determined by the valence of the metal, and x is a contained crystal water) or a double salt containing the compound, specifically, water Calcium oxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, barium hydroxide, zirconium hydroxide, dosonite, zinc stannate, zinc borate, aluminum borate, basic zinc carbonate, borax, zinc molybdate, Examples thereof include zinc phosphate, magnesium phosphate, hydrotalcite, hydrocalumite, kaolin, talc, sericite, pyrophyllite, bentonite, kaolinite, calcium sulfate, and zinc sulfate.
[0069]
Nitrogen-containing flame retardants include melamine, melamine cyanurate, methylolated melamine, (iso) cyanuric acid, melam, melem, melon, succinoguanamine, melamine sulfate, acetoguanamine sulfate, melam sulfate, guanylmelamine sulfate, melamine resin, BT Resins, cyanuric acid, isocyanuric acid, isocyanuric acid derivatives, melamine derivatives such as melamine isocyanurate, benzoguanamine, acetoguanamine, and guanidine compounds.
[0070]
Examples of phosphorus flame retardants include triethyl phosphate, tricresyl phosphate, triphenyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diethylene phosphate ethyl ester, dihydroxypropylene phosphate butyl ester, ethylene phosphate diester. Sodium ester, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methyl-propylphosphonic acid, t-butylphosphonic acid, 2,3-dimethylbutylphosphonic acid, octyl Phosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenyl Sphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, ammonium phosphate, ammonium polyphosphate, melamine phosphate, guanylurea phosphate, melamine polyphosphate, guanidine phosphate, ethylenediamine phosphate Examples include salts, phosphazenes, and melamine methylphosphonate.
[0071]
One or more of the other flame retardants described above are used, and among these, a hydrated metal compound is preferred. The amount of the other flame retardant added is 10 to 100 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of stabilized red phosphorus. In addition, although the particle size etc. of these other flame retardants do not have a restriction | limiting in particular, the average particle diameter normally calculated | required from a laser diffraction method is 100 micrometers or less, Preferably it is 1-30 micrometers.
[0072]
Moreover, the polymeric material composition containing the stabilized red phosphorus of the present invention can be used by blending other components depending on the intended use. Other components include, for example, phosphorus-based, ionic-based, hindered phenol-based antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, dyes, colorants including pigments, crosslinking agents, softening agents Examples thereof include, but are not particularly limited to, these additives.
[0073]
Further, if necessary, fibrous and / or granular fillers can be added to greatly improve the rigidity of the resin. Examples of such fillers include glass fibers, carbon fibers, metal fibers, aramid resins, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, calcium silicate, Examples include barium sulfate, titanium oxide, fused silica, crystalline silica, magnesia, and aluminum oxide.
Other components and fillers to be blended in the above-described polymer material may be blended in proportions that are usually used according to the type of resin that is usually used and the application of the resin.
[0074]
The method of mixing the stabilized red phosphorus of the present invention with the polymer material is not particularly limited, and may be required after previously mixing other flame retardants and other compounding agents as necessary. For example, after mixing while heating, there are a master batch method of mixing with other components and a method of mixing and mixing as it is, but which method to use is appropriately selected from industrially advantageous methods Good.
[0075]
The polymer material composition containing the stabilized red phosphorus in the present invention can be usually molded by a known method, for example, injection molding, extrusion molding, compression molding, blow molding, vacuum molding, press molding, calendar molding, By performing foam molding or the like, it can be formed into molded products of any shape such as sheets and films. These molded products include, for example, laminated plates, sealing materials, flat cables, wire cable covering materials, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, Variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display component, FDD carriage , FDD chassis, HDD parts, motor brush holder, parabolic antenna, electric / electronic parts represented by computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, Sound equipment parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home electronics, office computer parts, telephone related parts Parts, facsimile-related parts, copier-related parts, cleaning jigs, oil-less bearings, stern bearings, underwater bearings and other bearings, motor-related parts such as motor parts, lighters, typewriters, microscopes, binoculars , Optical devices such as cameras and watches, precision machinery related parts, alternator terminals, alternator connectors, IC regulators, light dial potentiometer bases, exhaust gas valves and other valves, fuel-related / exhaust / intake-system pipes Air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air Flow meter, Brake butt wear sensor, Thermostat base for air conditioner, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Dust distributor, starter switch, starter relay, transmission Wire harness, window washer nozzle, air conditioner panel switch H circuit board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, wallpaper However, the present invention is not particularly limited thereto.
[0076]
【Example】
  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
  In addition, although Examples 1-5 are shown below, in those Examples, Examples 2-4 show the Example of this invention, Example 1 and Example 5 show a reference example.
[0077]
<Coarse red phosphorus particles>
Coarse red phosphorus powder obtained by converting yellow phosphorus was used as the coarse red phosphorus particles as a raw material for production. The physical properties are shown in Table 1.
[0078]
[Table 1]

[0079]
In addition, the particle size distribution was measured with a laser diffraction particle size measuring device (manufactured by Seishin Enterprise Co., Ltd., model LMS-24 type).
The iron content was measured by acid decomposition thioglycolic acid spectrophotometry.
Yellow phosphorus was measured by a phospho-vanadium molybdic acid spectrophotometric method after benzene extraction.
[0080]
Example 1
In Example 1, the experiment was performed using the experimental apparatus of FIG. This experimental apparatus includes a container 1 storing a slurry containing coarse red phosphorus particles, a bead mill 2 of a wet pulverizer, a container 3 for temporarily storing the slurry discharged from the bead mill 2, and a liquid of two machines. Cyclones 4-1 and 4-2, an upper container 5 for storing the solution discharged from the upper part of the liquid cyclone, and a lower container 6 for storing the solution discharged from the lower part of the liquid cyclone are provided.
[0081]
(First step)
A slurry in which 10 kg of the above massive red phosphorus was dispersed in 10,000 kg of water was prepared and stored in the container 1 of FIG.
Next, the slurry prepared above was supplied to a ball mill (manufactured by Imex Corp .; type NVM5) 2 having a capacity of 5 L in which 6 kg of glass beads having a particle diameter of 0.6 mm were stored, and wet pulverization was performed. Table 2 shows various physical properties of the slurry containing red phosphorus particles stored in the container 3 after the wet pulverization treatment.
The wet pulverization conditions were as follows: the raw slurry charge amount was 3 L / min, and the rotor rotation speed was 800 rpm.
[0082]
In addition, content of each particle | grain and content of iron and yellow phosphorus show content contained in the dry red phosphorus powder which solid-liquid-separates a part of slurry. The particle size characteristics and the contents of iron and yellow phosphorus were determined by the same method as described above.
[0083]
[Table 2]

[0084]
(Second step)
500 kg of the slurry after the first step was supplied to a hydrocyclone (manufactured by Sanjo Iron Works) 4-1 and 4-2. Table 3 shows the physical properties of the slurry stored in the lower container 6 discharged from the bottom of the hydrocyclone 4-2, the time required for the treatment, and the removal rate of red phosphorus particles less than 5 μm.
[0085]
The removal rate of red phosphorus particles less than 5 μm was determined by the following formula (1).
[0086]
[Expression 1]

[0087]
(Where α is the content (% by weight) of particles less than 5 μm in the total amount of red phosphorus particles before being supplied to the liquid cyclone, and β is the amount of particles less than 5 μm in the total amount of red phosphorus particles after the liquid cyclone treatment. The content (% by weight) is indicated.)
[0088]
In addition, content of each particle | grain and content of iron and yellow phosphorus show content contained in the dry red phosphorus powder which solid-liquid-separates a part of slurry. The particle size characteristics and the contents of iron and yellow phosphorus were determined by the same method as described above.
[0089]
Moreover, the liquid cyclone used was a liquid cyclone having the structure shown in FIG.
-Cylindrical inner diameter (a): 56.5 mm
-Angle of inclination of conical portion (d): 21.2 degrees
-Length of upper cylindrical part (b): 58 mm
-Length of lower cone part (c): 135 mm
-Tube diameter (f) at the upstream extraction part: 11.8mm
-Tube diameter (e) at the downstream extraction part: 5 mm
The operating conditions are as follows.
・ Infeed pressure: 0.05 MPa
・ Flow distribution ratio (upstream / downstream); 2/1
[0090]
Comparative Example 1
After carrying out the first step in the same manner as in Example 1, 500 kg of the slurry containing the red phosphorus particles obtained was put into a separately prepared cylindrical tank (capacity 2000 L) with a stirrer, and stirred for 30 minutes, and stirring was stopped. The operation of replenishing, extracting 2/3 of the upper part of the slurry in the cylindrical tank, and replenishing the water of the extracted water was repeated 6 times to carry out fine particle cutting (cutting point 5 μm) by the tank decantation method. In addition, the total amount of the slurry extracted by six discharges was 400 kg.
[0091]
Further, a part of the slurry containing the red phosphorus particles present in the tank after being extracted six times is solid-liquid separated to obtain a dried red phosphorus powder, and the content of each particle contained in the dried red phosphorus powder The iron and yellow phosphorus contents were measured in the same manner as in Example 1. Table 3 shows the results, the time required for the treatment, and the removal rate of red phosphorus particles of less than 5 μm.
[0092]
In addition, the removal rate was calculated | required in the following formula (2).
[0093]
[Expression 2]

[0094]
(Α in the formula₁ Is the content (% by weight) of particles less than 5 μm in the total amount of red phosphorus particles before performing the tank decantation method, β₁ Indicates the content (% by weight) of particles less than 5 μm in the total amount of red phosphorus particles after the tank decantation method. )
[0095]
Comparative Example 2
After carrying out the first step in the same manner as in Example 1, a 500 L overflow experiment tank (countercurrent contact washing tank, upper part: cylindrical type, lower part) separately prepared 500 kg of slurry containing red phosphorus particles obtained : Inverted cone type), and fine particles were cut by a method (water tank method) in which water was fed from the bottom with a metering pump to overflow only the fine particles. At this time, the slurry recovered by overflowing was 2000 kg.
[0096]
Further, a part of the slurry containing red phosphorus particles in the overflow experiment tank after the water tank method was subjected to solid-liquid separation to obtain a dried red phosphorus powder. The content of each particle contained in the dry red phosphorus powder and the content of iron and yellow phosphorus were measured in the same manner as in Example 1. Table 3 shows the results, the time required for the treatment, and the removal rate of red phosphorus particles of less than 5 μm.
[0097]
In addition, the removal rate was calculated | required in the following formula (3).
[0098]
[Equation 3]

[0099]
(Α in the formula₂ Is the content (% by weight) of particles less than 5 μm in the total amount of red phosphorus particles before carrying out the elutriation method, β₂ Indicates the content (% by weight) of particles less than 5 μm in the total amount of red phosphorus particles after the elutriation method. )
[0100]
[Table 3]

[0101]
From the results in Table 3, it can be seen that red phosphorus particles of less than 5 μm can be efficiently removed in a short time by using a liquid cyclone as a means for removing red phosphorus particles of less than 5 μm.
[0102]
<Measurement of phosphine gas generation amount>
0.5 g of red phosphorus obtained by solid-liquid separation from the slurry of Example 1 and Comparative Examples 1 and 2 and drying was collected on an alumina board, placed in a test tube, and heated in nitrogen gas at 250 ° C. for 1 hour. . Generated PH_Three The amount was collected in a tedlar bag and measured with a detector. The results are shown in Table 4.
[0103]
<Measurement of phosphorus oxoacid elution amount>
8 g of red phosphorus obtained by solid-liquid separation from the slurry of Example 1 and Comparative Examples 1 and 2 and drying was collected in a 100 ml polypropylene bottle, and 80 ml of distilled water was added and sealed. After heating and extraction at 80 ° C. for 20 hours in a blast constant temperature dryer, the product is taken out from the dryer, cooled to room temperature within 10 minutes, filtered the supernatant, and then eluted PO in the filtrate._Four Ion, PHO_Three Ion and PH₂ O₂ The concentration of ions was measured with an ion chromatograph. The results are shown in Table 4.
[0104]
[Table 4]

[0105]
From the results in Table 4, it can be seen that the amount of phosphine generated and the amount of phosphorus oxoacid eluted are reduced when red phosphorus particles of less than 5 μm are reduced to 5% by weight or less of the total amount of red phosphorus.
[0106]
Example 2 and Comparative Examples 3-4
Water was added to the slurry containing the red phosphorus particles obtained in Example 1 and Comparative Examples 1 and 2 to make a 10% slurry, and 0.7 ml of a 30% aqueous hydrogen peroxide solution was added to 735 g of this slurry. Next, the pH was adjusted to 10 with an aqueous sodium hydroxide solution and kept at 80 ° C. for 6 hours. Nitric acid was then added to adjust the pH to 1, followed by treatment at 80 ° C. for 4 hours, followed by filtration and washing with water until the pH of the slurry was 8.
[0107]
Next, some red phosphorus particles were recovered from the obtained slurry, and after drying, iron and yellow phosphorus were measured in the same manner as in Example 1. The results are shown in Table 5. In addition, PH can be obtained in the same manner as in Example 1._Three The amount generated and the amount of phosphorus oxoacids eluted were measured. The results are shown in Table 5.
[0108]
[Table 5]

[0109]
From the results of Table 5, the amount of phosphine generated and the amount of phosphorus oxoacid eluted can be reduced by reducing the content of iron and yellow phosphorus by subjecting the slurry containing red phosphorus particles to acid treatment and alkali treatment. I understand that I can do it.
[0110]
Example 3 and Comparative Examples 5-6
Water was added to the slurry obtained in Example 2 and Comparative Examples 3 and 4 to prepare a 10% slurry.₂ O_Three Was added to 48.9 g of 8 wt% aluminum sulfate, adjusted to pH 8 with 2.9 wt% aqueous ammonia with stirring, and aged at 80 ° C. for 3 hours.
[0111]
After standing to cool, it filtered with the centrifugal filter and collect | recovered covering red phosphorus from the reaction liquid. This coated red phosphorus is again added to form a slurry, which is then repulped by a conventional method, and washed until the electrical conductivity at 25 ° C. when the coated red phosphorus is 10% slurry is 30 μs / cm or less. did. The washed coated red phosphorus was dried under reduced pressure at 110 ° C. for 6 hours to obtain stabilized red phosphorus. Table 6 shows the physical properties of the obtained stabilized red phosphorus.
[0112]
[Table 6]

[0113]
(Note) The electric conductivity in Table 6 is the value of 10% slurry of stabilized red phosphorus at 25 ° C. The electrical conductivity is a value obtained by an electrical conductivity meter using a test solution for measuring eluted ions.
[0114]
<Measurement of phosphine gas generation amount>
0.5 g of each of the stabilized red phosphorus obtained in Example 3 and Comparative Examples 5 to 6 was collected on an alumina board, placed in a test tube, and heated in nitrogen gas at 250 ° C. for 1 hour. Generated PH_Three The amount was collected in a tedlar bag and measured with a detector. The results are shown in Table 7.
[0115]
<Measurement of phosphorus oxoacid elution amount>
8 g of each stabilized red phosphorus obtained in Example 3 and Comparative Examples 5 to 6 is collected in a 100 ml polypropylene bottle, and 80 ml of distilled water is added and sealed. After heating and extraction at 80 ° C. for 20 hours in a blast constant temperature dryer, the product is taken out from the dryer, cooled to room temperature within 10 minutes, filtered the supernatant, and then eluted PO in the filtrate._Four Ion, PHO_Three Ion and PH₂ O₂ The concentration of ions was measured with an ion chromatograph. The results are shown in Table 7.
[0116]
[Table 7]

[0117]
From the results of Table 7, it can be seen that in the production method of the present invention, the amount of phosphine generated and the amount of phosphorus oxoacid eluted are reduced as compared with the comparative example.
[0118]
Example 4
In Example 4, the experiment was performed using the experimental apparatus of FIG. This experimental apparatus is composed of a container 1 storing a slurry containing coarse red phosphorus particles, a tower mill 7 of a wet pulverizer, a sieve 8 having a sieve opening size of 75 μm, and a slurry passed through the sieve 8 temporarily. A container 3 for storing the liquid, 2 liquid cyclones 4-1 and 4-2, an upper container 5 for storing the solution discharged from the top of the liquid cyclone 4-2, and the opening size of the sieve is 45 μm. And a lower container 6 for storing the slurry that has passed through the sieve 9.
[0119]
The pulverized product pulverized by the tower mill 7 is sent to the sieve 8 due to overflow, and particles larger than 75 μm are sent again to the tower mill. On the other hand, the particles that have passed through the sieve 8 are stored in the container 3 for temporary storage. Further, the slurry discharged from the lower part of the hydrocyclone 4-2 passes through the sieve 9 and is stored in the lower container 6.
[0120]
(First step)
A slurry was prepared by dispersing 3300 kg (3.3 t) of the above-described coarse red phosphorus in 10000 L of water, adjusted to pH 3.5 by adding nitric acid thereto, and stored in the container 1.
Next, this slurry was introduced into a tower mill apparatus (model VW-15 manufactured by Nippon Tower Mill Co., Ltd.) 7 and wet pulverized. Table 8 shows various physical properties of the slurry containing the red phosphorus particles that passed through the sieve 8 and stored in the container 3. In addition, content of each particle | grain, content of iron and yellow phosphorus shows content contained in the red phosphorus powder which solid-liquid-separated a part of slurry and dried. The particle size characteristics and the contents of iron and yellow phosphorus were measured in the same manner as in Example 1.
[0121]
The operation conditions of the tower mill apparatus were as follows.
・ Size: Height 4.8m x Length 3.6m x Width 2.8m
・ Rotation speed: 60rpm
・ Crushing media: 2.5 cm diameter alumina balls
[0122]
[Table 8]

[0123]
(Second step)
Water was added to 300 kg of the slurry after the first step to adjust the specific gravity of the slurry to 1.04, and then this was supplied to liquid cyclones (manufactured by Sanjo Iron Works) 4-1 and 4-2. Table 9 shows the physical properties of the slurry discharged from the bottom of the hydrocyclone, passed through the sieve 9 having a sieve opening of 45 μm, and stored in the lower container 6 and the time required for processing.
[0124]
In addition, content of each particle | grain, content of iron and yellow phosphorus shows content contained in the red phosphorus powder which solid-liquid-separated a part of slurry and dried. The particle size characteristics and the contents of iron and yellow phosphorus were measured in the same manner as in Example 1.
[0125]
Moreover, the liquid cyclone used was a liquid cyclone having the structure shown in FIG.
-Cylindrical inner diameter (a): 56.5 mm
-Angle of inclination of conical portion (d): 21.2 degrees
-Length of upper cylindrical part (b): 58 mm
-Length of lower cone part (c): 135 mm
-Tube diameter (f) at the upstream extraction part: 11.8mm
-Tube diameter (e) at the downstream extraction part: 5 mm
The operating conditions are as follows.
・ Infeed pressure: 0.05 MPa
・ Flow distribution ratio (upstream / downstream); 2/1
[0126]
[Table 9]

[0127]
Next, water was added to the slurry containing red phosphorus particles obtained above to make a 10% slurry, and 0.7 ml of a 30% aqueous hydrogen peroxide solution was added to 735 g of this slurry. Next, the pH was adjusted to 10 with an aqueous sodium hydroxide solution and kept at 80 ° C. for 6 hours. Subsequently, nitric acid was added to adjust the pH to 1, followed by treatment at 80 ° C. for 4 hours, followed by filtration and washing with water until the pH of the 10% slurry was 8. A part of the slurry was solid-liquid separated and the content of iron and yellow phosphorus was measured in the same manner as in Example 1. The content of iron contained in the dried red phosphorus powder was 0.01% by weight, The yellow phosphorus content was 0.002% by weight.
[0128]
Next, the washed red phosphorus is made into a 10% slurry again, and 300 g of this slurry is mixed with Al.₂ O_Three Then, 1.2 g of aluminum sulfate containing 8% by weight was added, adjusted to pH 8 with 2.9% aqueous ammonia with stirring, and aged at 80 ° C. for 3 hours.
[0129]
After allowing to cool, the coated red phosphorus is recovered from the reaction solution by filtration according to a conventional method. After adding water again to form a slurry, the pulp is repulped by a conventional method to obtain a 10% slurry of the coated red phosphorus. Washing was performed until the electric conductivity was 1000 μs / cm or less.
[0130]
Next, the washed red phosphorus was again made into a 10% slurry, adjusted to pH 10 with 29 wt% ammonia water, and 6 g of phenol resin (manufactured by Dainippon Ink Co., Ltd., initial condensate, phenolite TD2388; solid content 25%) was added.
Subsequently, the pH was adjusted to 6.5 using hydrochloric acid, and then a curing reaction was performed at 90 ° C. for 1 hour.
[0131]
After allowing to cool, the slurry is sufficiently filtered and washed, and the filter cake is dried under reduced pressure, then cured at 140 ° C. for 1 hour, allowed to cool and then passed through a 100 mesh sieve to stabilize the red phosphorus sample Got. Table 10 shows the physical properties of the obtained stabilized red phosphorus. Further, the amount of phosphine gas generated and the amount of phosphorus oxoacid eluted were measured in the same manner as in Example 3. The results are shown in Table 10.
[0132]
[Table 10]

[0133]
(Note) The electric conductivity in the table is the value of 10% slurry of stabilized red phosphorus at 25 ° C.
[0134]
Example 5
In Example 5, slurry production was performed 5 times using the experimental apparatus shown in FIG. 3, and quality stability was evaluated.
[0135]
(First to second step)
A slurry was prepared by dispersing 3300 kg (3.3 t) of the above-mentioned coarse red phosphorus in 10000 L of water, adjusted to pH 3.5 by adding nitric acid thereto, and stored in the container 1 in FIG.
[0136]
Next, this slurry is introduced into a tower mill device (model VW-15 manufactured by Nippon Tower Mill Co., Ltd.), subjected to a wet pulverization treatment, and then passed through a sieve 8 to a slurry containing red phosphorus particles stored in the container 3. Water having a specific gravity of 1.04 is added to the hydrocyclone (manufactured by Sanjo Iron Works) 4-1 and 4-2, and the slurry discharged from the bottom of the hydrocyclone and passed through the sieve 9 is placed in the lower container. 6 stored. As a result, a first slurry was obtained.
[0137]
As in the first slurry, the second slurry uses the slurry in which 3300 kg of coarse red phosphorus is dispersed in 10000 L of water, and the first to second steps as in the first. The second slurry was obtained.
Similarly, the operation from the first step to the second step was performed 5 times in total, and the particle size characteristics of the red phosphorus particles contained in each slurry stored in the lower container 6 were measured in the same manner as in Example 1. The results are shown in Table 11.
The time required for the processing in the second step is also shown in Table 11 together.
[0138]
The operating conditions of the tower mill device are as follows.
・ Size: Height 4.8m x Length 3.6m x Width 2.8m
・ Rotation speed: 60rpm
・ Crushing media: 2.5 cm diameter alumina balls
[0139]
Moreover, the liquid cyclone used was a liquid cyclone having the structure shown in FIG.
-Cylindrical inner diameter (a): 56.5 mm
-Angle of inclination of conical portion (d): 21.2 degrees
-Length of upper cylindrical part (b): 58 mm
-Length of lower cone part (c): 135 mm
-Tube diameter (f) at the upstream extraction part: 11.8mm
-Tube diameter (e) at the downstream extraction part: 5 mm
The operating conditions of the hydrocyclone are as follows.
[0140]
・ Infeed pressure: 0.05 MPa
・ Distribution ratio (upstream / downstream); 2/1
[0141]
[Table 11]

[0142]
From the results of Table 11, it can be seen that the method for producing a slurry containing red phosphorus particles of the present invention can produce a stable quality product in a short time.
[0143]
【The invention's effect】
As described above, according to the method for producing a slurry containing red phosphorus particles of the present invention, an industrially advantageous method containing red phosphorus particles with less generation of phosphine gas and further less phosphorus oxoacid elution. The slurry can be obtained in a short time and with stable quality.
[0144]
Further, according to the method for producing stabilized red phosphorus of the present invention, the red phosphorus particles obtained by the method for producing a slurry containing the above-mentioned red phosphorus particles are used as production raw materials, and the generation amount of phosphine gas and phosphorus It is possible to obtain stabilized red phosphorus in which the amount of oxo acid eluted is effectively suppressed.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a typical structure of a hydrocyclone used in the present invention.
FIG. 2 is a schematic view showing an experimental apparatus used in the first step and the second step of Example 1 of the present invention.
FIG. 3 is a schematic view showing an experimental apparatus used in the first step and the second step of Examples 4 and 5 of the present invention.
[Explanation of symbols]
a Cylindrical inner diameter of hydrocyclone
b Length of upper cylindrical part of hydrocyclone
c Length of the lower cone of the hydrocyclone
d Angle of inclination of conical part of hydrocyclone
e Pipe diameter of the downstream extraction part of the hydrocyclone
f Pipe diameter of upstream extraction part of hydrocyclone
P pump
1 container
2 Bead mill
3 containers
4-1 4-2 Hydrocyclone
5 Upper container
6 Lower container
7 Tower mill
8 Sieve with sieve opening of 75μm
9 Sieve sieve opening size 45μm

Claims (8)

A slurry containing raw material red phosphorus particles containing iron and yellow phosphorus as impurities is wet-ground, and the content of red phosphorus particles having a particle size of 45 μm or less contained in the slurry is 50% by weight of the total amount of red phosphorus particles. The first step of preparing the slurry as described above, and the slurry prepared in the first step is treated with a hydrocyclone, and the content of red phosphorus particles having a particle size of less than 5 μm contained in the slurry is reduced to red phosphorus particles The second step of preparing a slurry having an average particle size of 10 to 40 μm with 5% by weight or less of the total amount, further before the first step, after the first step, and at any time after the second step The red phosphorus particles are treated by adding acid and alkali to the slurry containing the particles, and the content of iron of impurities contained in the red phosphorus particles is 0.1 wt% or less and the content of yellow phosphorus is 0.005 wt. % red phosphorus particles, which comprises a step of reducing below Method of manufacturing a slurry containing.   The method for producing a slurry containing red phosphorus particles according to claim 1, wherein the wet pulverization treatment in the first step is performed using a tower mill.   The method for producing a slurry containing red phosphorus particles according to claim 2, wherein the wet pulverization treatment in the tower mill is performed in the presence of nitric acid.   The method for producing a slurry containing red phosphorus particles according to any one of claims 1 to 3, further comprising a step of removing red phosphorus particles having a particle size exceeding 45 µm from the slurry after the second step.   The method for producing a slurry containing red phosphorus particles according to claim 4, wherein the removal of the red phosphorus particles having a particle size of more than 45 µm is performed by a sieve. The slurry containing red phosphorus particles produced by the method according to any one of claims 1 to 5 is at least one water-soluble substance selected from Zn, Al, Mg, Ti, Si, Co, Zr, and Sn. A stabilized red phosphorus having a step of preparing an aqueous suspension by adding a metal salt and a step of adding an alkali to the aqueous suspension to precipitate the metal salt on the surface of the red phosphorus particles. Production method. A step of solid-liquid separation of the slurry containing red phosphorus particles produced by the method according to any one of claims 1 to 5 to obtain red phosphorus particles, and a slurry containing the obtained red phosphorus particles are prepared. And adding at least one water-soluble metal salt selected from Zn, Al, Mg, Ti, Si, Co, Zr, and Sn to the slurry containing the red phosphorus particles to form an aqueous suspension. A method for producing stabilized red phosphorus, comprising a step of preparing, and a step of adding an alkali to the aqueous suspension to precipitate a metal salt on the surface of the red phosphorus particles. A stabilized red phosphorus characterized by adding a raw material for synthesizing a thermosetting resin or an initial condensate thereof to a slurry containing the stabilized red phosphorus produced by the method according to claim 6 or 7. Manufacturing method.

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