JP4238011B2 - Method for producing metal sulfide - Google Patents

Description

【００５１】
（数式中、Ｎｉは、金属Ｍｉの原子価（価数）を表す。また、Ｘｉは、金属アルコキシ基含有化合物として用いた金属元素Ｍｉのモル数を表す。ｐは２以上の整数である。）
から算出することができる。また、前記カルボキシル基含有化合物の総量に含まれるカルボキシル基の数が、前記金属アルコキシ基含有化合物の総量に含まれるアルコキシ基の数Ｎ’に対して、０．８Ｎ’超であることも好ましく、１Ｎ’〜１０Ｎ’が特に好ましい。なお、数値範囲を表す際に、数値の後ろに「超」と付した場合は、その数値を含まずそれより大きい数値範囲を示すものとする。
【００５２】
組み合わせＣおよび組み合わせＤにおける還元性物質としては、特に制限はなく、従来公知の還元性物質を用いることができる。具体的には、例えば、ホルムアルデヒド；ヒドラジン、ヒドラジン誘導体等のヒドラジン化合物；水素化ホウ素ナトリウム等の金属水素化ホウ素塩；クエン酸、クエン酸金属塩等のクエン酸化合物；コハク酸、コハク酸金属塩等のコハク酸化合物；アミノ基含有化合物；Ｓｎ（II）やＭｎ（II）などの低原子価金属の化合物；単糖類、多糖類等の糖類；等が挙げられる。また、これら液体や固体のものの他に、水素ガスなどの還元性ガスも還元性物質として用いることができる。これらの中でも特に、安全性および得られる金属硫化物粒子や金属硫化物膜の機能を阻害しにくい点からは、クエン酸化合物、コハク酸化合物、アミノ基含有化合物、低原子価金属の化合物が好ましい。また、還元性物質としては、後述する塩基性物質としても作用しうるもの（後述する塩基性物質と同様のもの）が好ましく、中でも、アルカノールアミンが好ましい。なお、還元性物質は、１種のみを用いてもよいし、２種以上を併用してもよい。
【００５３】
前記アミノ基含有化合物としては、具体的には、例えば、１〜３級のアミノ基を含有する化合物や、４級アンモニウム基を含有する化合物などが挙げられ、具体的には、メチルアミン、イソブチルアミン、ジブチルアミン、トリブチルアミン、エチル−ｎ−ブチルアミン、ｔｅｒｔ−ブチルアミン、ラウリルアミン、ステアリルアミン、Ｎ−ドデシル−１−ドデカンアミン、Ｎ，Ｎ−ジオクチル−１−オクタンアミン、Ｎ，Ｎ−ジメチル−１−オクタデカンアミン、シクロヘキシルアミン、ジシクロヘキシルアミン等の１級、２級または３級の脂肪族アミン、エチレンジアミン、Ｎ−オクタデシル−１，３−プロパンジアミン等の脂肪族ジアミン、トリアミン、ポリエチレンイミン等のポリアミン、モルフォリン、ピペラジン等の脂肪族環状アミンなどの脂肪族アミン；Ｎ−フェニルヒドロキシルアミン、ｐ−（ヒドロキシアミノ）フェノール、モノエタノールアミン、トリエタノールアミン等の脂肪族または芳香族ヒドロキシルアミン；アニリン、Ｎ−メチルアニリン、Ｎ、Ｎ−ジメチルアニリン、ジフェニルアミン、Ｎ−エチル−Ｎ−フェニルベンジルアミン、ｏ−トルイジン、ｐ−トルイジン、２，３−キシリジン、ｏ−アニシジン、ジアミノトルエン、４，４−メチレンジアニリン、フェニレンジアミン等の芳香族アミン；水酸化テトラメチルアンモニウム、水酸化トリメチルベンジルアンモニウム、テトラブチルアンモニウムハイドロゲンサルフェート、臭化トリメチルフェニルアンモニウム、臭化テトラメチルアンモニウム、臭化テトラ−ｎ−ブチルアンモニウム、Ｎ−ベンジルピコリニウムクロライド、ヨウ化テトラメチルアンモニウム、Ｎ−ラウリル４−ピコロニウムクロライド、塩化トリメチルベンジルアンモニウム、塩化Ｎ−ラウリルピリジニウム、塩化トリブチルベンジルアンモニウム、塩化トリオクチルメチルアンモニウム、塩化テトラメチルアンモニウム、塩化トリエチルペンジルアンモニウム等の第４級アンモニウム塩；等が挙げられる。これらの中でも特に、低温で金属硫化物を生成させやすい点からは、ヒドロキシルアミンが好ましい。
【００５４】
前記低原子価金属の化合物としては、具体的には、例えば、金属イオン；水酸化物；酸化物；硝酸塩、塩化物、炭酸（水素）塩、カルボン酸塩等の塩；金属アルコキシド；金属アセチルアセテートなどのβ−ジケトン錯体、β−ケトエステル錯体等の有機金属錯体；等が挙げられ、これらの金属元素としては、Ｓｎ、Ｍｎ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｒｅ、Ｉｎ、Ｔｌ、Ｓｂ等が挙げられる。
組み合わせＣおよび組み合わせＤにおける還元性物質の使用量については、前記出発原料に含まれる金属原子（カチオン状態）を金属に還元するのに必要な量が少なくとも存在すればよく、特に限定はないが、前記出発原料に含まれる金属原子Ｘの原子価をｎとして、還元性物質／金属原子Ｘ（モル比）が０．５ｎ〜５ｎとなるようにすることが好ましい。
【００５５】
本発明の第２の製造方法においては、前記還元性物質は、前記出発原料（金属カルボン酸塩とアルコール、または、金属アルコキシ基含有化合物とカルボキシル基含有化合物）の混合以前に前記出発原料の少なくとも１つに添加するようにする。すなわち、前記出発原料となる２つの混合前または混合と同時に、前記還元性物質を前記出発原料となる２つのうちの少なくとも一方に添加するのであり、言い換えれば、前記出発原料となる２つが混合された状態においては必ず前記還元性物質を併存させるようにすることが重要となるのである。したがって、前記出発原料の混合系には、前記出発原料のほかに、前記還元性物質（後述するように前記混合系が予備反応物になっている場合、該還元性物質由来の物質に変化していてもよい）は必ず含まれることとなる。本発明の第２の製造方法においては、前記出発原料となる２つと還元性物質との３成分によって一旦金属が生成し、該金属が後述するチオール化合物と反応することにより金属硫化物が生成するものと推測される。
【００５６】
組み合わせＣおよび組み合わせＤにおけるチオール化合物としては、例えば、本発明の第１の製造方法において組み合わせＡのＡ２成分として例示したものと同様のものが挙げられる。なお、チオール化合物は、１種のみを用いてもよいし、２種以上を併用してもよい。
組み合わせＣおよび組み合わせＤにおけるチオール化合物の使用量については、特に限定はなく、金属カルボン酸塩または金属アルコキシ基含有化合物の有する金属原子の総数に対するチオール化合物中のチオール基の総数のモル比（チオール基／金属原子）が、得ようとする金属硫化物における硫黄原子（Ｓ）と金属原子（Ｍ）とのモル比（金属硫化物Ｓ／Ｍ比）と同等以上になるようにすればよいのであるが、通常は、金属硫化物Ｓ／Ｍ比の１〜５倍となるようにすることが好ましい。
【００５７】
本発明の第２の製造方法においては、前記チオール化合物は、前記還元性物質の添加と同時かまたはその後に、前記出発原料（金属カルボン酸塩とアルコール、または、金属アルコキシ基含有化合物とカルボキシル基含有化合物）の少なくとも１つに添加するようにし、該添加後、前記出発原料の混合系を高温状態にする。すなわち、前記出発原料の混合系を高温状態にする時点では、該混合系に必ず前記チオール化合物が併存するようにすることが重要となるのである。したがって、前記出発原料の混合系には、前記チオール化合物（後述するように前記混合系が予備反応物になっている場合、該チオール化合物由来の化合物に変化していてもよい）は必ず含まれることとなる。
【００５８】
本発明の第２の製造方法においては、前記出発原料の混合系を高温状態にすることにより、金属硫化物を生成させる。
本発明の第２の製造方法において、前記出発原料の混合系とは、前述のように、前記組み合わせＣまたは組み合わせＤを必須とする原料の混合系のことであり、前記組み合わせＣまたは組み合わせＤを必須とする原料を混合してなる混合物、および／または、前記組み合わせＣまたは組み合わせＤを必須とする原料から得られる予備反応物を意味するものである。なお、前記混合系は、その一部が予備反応物であり、その他が前記出発原料の混合物となっていてもよい。
【００５９】
前記予備反応物は、前記組み合わせＣにおける金属カルボン酸塩とアルコールと還元性物質とチオール化合物との反応による反応物、または組み合わせＤにおける金属アルコキシ基含有化合物とカルボキシル基含有化合物と還元性物質とチオール化合物との反応による反応物として、金属硫化物が生成されるまでの任意の段階の状態（金属硫化物の生成が認められる前の状態）の反応中間体であり、生成される金属硫化物に対する前駆体（金属硫化物前駆体）である。すなわち、予備反応物は、前述した各原料のいずれでもなく、生成される金属硫化物でもない、金属硫化物前駆体である。このような予備反応物は、例えば、各原料を混合するだけで直ちに得られるか、各原料の混合物を緩やかな高温状態（金属硫化物が得られる温度よりも低い温度である状態）にすることにより得られる。
【００６０】
前記混合系は、ペースト状、懸濁液状、溶液状などの流動性のある液状であることが好ましく、必要に応じて、出発原料として反応溶媒をも用いるようにしてもよい。具体的には、組み合わせＣまたは組み合わせＤからなる各原料の一部または全部を混合するにあたり、あるいは、これら原料からなる混合系を高温状態にするにあたり、さらに反応溶媒を加えた上で行うようにすればよい。
前記反応溶媒をも用いる場合、その使用量については、特に限定はないが、経済的に金属硫化物を得ることを考慮すると、金属カルボン酸塩または金属アルコキシ基含有化合物の使用量が、該反応溶媒を含めた全重量に対して０．１〜５０重量％となるようにすることが好ましい。
【００６１】
前記反応溶媒としては、水以外の溶媒、すなわち、非水溶媒が好ましい。非水溶媒の具体例としては、本発明の第１の製造方法において例示したものと同様である。
組み合わせＣの場合の反応溶媒としては、特に、前述した非水溶媒のなかでも、アルコール系溶媒が好ましく、必須の出発原料であるアルコールとして用いられるアルコールを溶媒とすればよい。
組み合わせＤの場合の反応溶媒として好ましい具体例としては、本発明の第１の製造方法において組み合わせＢの場合に好ましい反応溶媒として例示したものと同様である。
【００６２】
金属硫化物を生成させる際には、前記混合系に含まれる水分は少ない方が、得られる金属硫化物の欠陥が少なくなるため好ましい。具体的には、組み合わせＣを原料とする場合には、前記混合系中の水分／金属カルボン酸塩中の金属原子（モル比）が４未満のわずかな水分しか含有しないことが好ましく、前記モル比が１未満であるとさらに好ましく、０．５未満であると特に好ましい。一方、組み合わせＤを原料とする場合には、前記混合系中の水分／金属アルコキシ基含有化合物中の金属原子（モル比）が１未満のわずかな水分しか含有しないことが好ましく、前記モル比が０．２未満であるとさらに好ましく、０．１未満であると特に好ましい。
【００６３】
本発明の第２の製造方法において、前記混合系を高温状態にするとは、前記混合系の温度を常温よりも高い温度（金属硫化物が生成する温度）にまで昇温することである。高温状態の温度（金属硫化物が生成する温度）は、得ようとする金属硫化物の種類等によって異なるが、通常５０℃以上であり、結晶性の高い金属硫化物を得るためには、１００℃以上が好ましく、さらに１００〜３００℃の範囲であるのが好ましい。特に、後述するように金属硫化物を膜として得ようとする場合であって基材として高分子フィルム等の有機物の基材を用いる場合には、１００〜２００℃の範囲であるのが好ましく、より好ましくは１００〜１５０℃の範囲である。
【００６４】
前記混合系を高温状態にする際の具体的な昇温手段（予備反応物を得る場合に緩やかな高温状態にする際の昇温手段も含む）としては、ヒーター、温風や熱風による加熱が一般的であるが、これに制限されるものではなく、例えば、紫外線照射などの手段を採用することもできる。加熱により高温状態にする場合は、常圧下、加圧下、減圧下のいずれの圧力下で行ってもよく、特に限定はされないが、反応溶媒等の沸点が金属硫化物の生成する温度よりも低い場合は、耐圧反応装置を用いて行うことも好ましい。通常、反応温度、反応時の気相圧は、溶媒となる成分の臨界点以下で行うが、超臨界条件で行うこともできる。
【００６５】
本発明の第２の製造方法においては、前記高温状態において前記混合系に塩基性物質を存在させるようにすることが好ましい。これにより、金属硫化物をより低温で生成させることができる。
前記塩基性物質としては、例えば、アミノ基含有化合物；アルカリ金属やアルカリ土類金属の金属イオン；水酸化物；酸化物；炭酸（水素）塩、カルボン酸塩等の弱酸の塩；アルカリ金属やアルカリ土類金属の金属アルコキシド；アルカリ金属やアルカリ土類金属の金属アセチルアセテナートなどのβ−ジケトン錯体、β−ケトエステル錯体等の有機金属錯体；等が好ましく挙げられる。なお、アミノ基含有化合物としては、還元性物質として例示したものと同様のものが挙げられる。これらの中でも、アルカノールアミンが特に好ましい。なお、塩基性物質は、１種のみを用いてもよいし、２種以上を併用してもよい。
【００６６】
前記塩基性物質の使用量については、特に限定はないが、金属カルボン酸塩または金属アルコキシ基含有化合物の有する金属原子の総モル数に対して、０．０１〜５倍モルとするのが好ましく、０．０５〜２倍モルとするのがより好ましい。
本発明の第２の製造方法において、前記混合系（前記組み合わせＣまたは組み合わせＤにおける各原料の混合物および／または前記組み合わせＣまたは組み合わせＤにおける各原料の予備反応物）を得る際の混合と、前記混合系を高温状態にする際の昇温（予備反応物を各原料の混合と、さらに緩やかな高温状態にすることとで得る場合において、緩やかな高温状態にする際の昇温も含む）とは、別々に行っても、同時（一部同時も含む）に行ってもよく、特に限定はされない。具体的には、例えば、１）各成分（組み合わせＣまたは組み合わせＤにおける各原料、および必要に応じて反応溶媒）を混合（還元性物質とチオール化合物については前述した順序に従い混合）した後、該混合物を所定温度に昇温する、２）アルコールもしくはカルボキシル基含有化合物を所定温度に昇温しておき、該温度を維持しながら、これにその他の原料を混合（還元性物質とチオール化合物については前述した順序に従い混合）する（この場合、反応溶媒は、金属カルボン酸塩もしくは金属アルコキシ基含有化合物とともに昇温してもよいし、その他の原料とともに混合してもよい）、３）反応溶媒と金属カルボン酸塩もしくは金属アルコキシ基含有化合物とを混合して所定温度に昇温しておき、該温度を維持しながら、これにその他の原料を混合（還元性物質とチオール化合物については前述した順序に従い混合）する、４）各成分（組み合わせＣまたは組み合わせＤにおける各原料、および必要に応じて反応溶媒）を別々に所定温度に昇温しておいた後、これらを混合（還元性物質とチオール化合物については前述した順序に従い混合）する、等が好ましく挙げられる。
【００６７】
＜第３の金属硫化物の製造方法＞
本発明の第３の金属硫化物の製造方法は、金属微粒子とチオール化合物を必須の出発原料とする。
前記金属微粒子としては、具体的には、例えば、１Ａ族、２Ａ族、３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、ランタノイド元素、アクチノイド元素、１Ｂ族、２Ｂ族、３Ｂ族、４Ｂ族、５Ｂ族、６Ｂ族に含まれる金属元素の金属微粒子を挙げることができる。これらの中でも、例えば、Ｓｒ、Ｃｅ、Ｙ、Ｔｉ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｎ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、ＳｂおよびＬａ等の金属元素からなる金属微粒子が好適である。また、前記金属微粒子として、合金微粒子を用いることもできる。これら金属微粒子は、１種のみを用いてもよいし、２種以上を併用してもよい。
【００６８】
前記金属微粒子は、微細であるほど、または多孔質であるほど（すなわち、比表面積が大きいほど）、短時間で金属硫化物の生成が完結し、粒子径の揃った超微粒子状の金属硫化物や、平坦性に優れた金属硫化物膜が得られる。したがって、前記金属微粒子としては、比表面積径が１００ｎｍ以下であるものが好ましく、２０ｎｍ以下のものがより好ましい。
前記チオール化合物としては、具体的には、例えば、本発明の第１の製造方法において組み合わせＡのＡ２成分として例示したものと同様のものが挙げられる。なお、チオール化合物は、１種のみを用いてもよいし、２種以上を併用してもよい。
【００６９】
前記金属微粒子とチオール化合物との使用量の割合については、特に限定はなく、金属微粒子の金属原子の総数に対するチオール化合物中のチオール基の総数のモル比（チオール基／金属原子）が、得ようとする金属硫化物における硫黄原子（Ｓ）と金属原子（Ｍ）とのモル比（金属硫化物Ｓ／Ｍ比）と同等以上になるようにすればよいのであるが、通常は、金属硫化物Ｓ／Ｍ比の１〜１００倍となるようにすることが好ましく、１〜５倍となるようにすることがより好ましい。
本発明の第３の製造方法においては、前記出発原料の混合系を高温状態にすることにより、金属硫化物を生成させる。
【００７０】
本発明の第３の製造方法において、前記出発原料の混合系とは、前記出発原料を混合してなる混合物、および／または、前記出発原料から得られる予備反応物を意味するものである。なお、前記混合系は、その一部が予備反応物であり、その他が前記出発原料の混合物となっていてもよい。
前記予備反応物は、前記金属微粒子とチオール化合物との反応による反応物として、金属硫化物が生成されるまでの任意の段階の状態（金属硫化物の生成が認められる前の状態）の反応中間体であり、生成される金属硫化物に対する前駆体（金属硫化物前駆体）である。すなわち、予備反応物は、金属微粒子、チオール化合物のいずれでもなく、生成される金属硫化物でもない、金属硫化物前駆体である。このような予備反応物は、例えば、金属微粒子とチオール化合物とを混合するだけで直ちに得られるか、金属微粒子とチオール化合物との混合物を緩やかな高温状態（金属硫化物が得られる温度よりも低い温度である状態）にすることにより得られる。
【００７１】
前記混合系は、ペースト状、懸濁液状、溶液状などの流動性のある液状であることが好ましく、必要に応じて、出発原料として反応溶媒をも用いるようにしてもよい。具体的には、金属微粒子とチオール化合物とからなる出発原料を混合するにあたり、あるいは、これら出発原料からなる混合系を高温状態にするにあたり、さらに反応溶媒を加えた上で行うようにすればよい。
前記反応溶媒をも用いる場合、その使用量については、特に限定はないが、経済的に金属硫化物を得ることを考慮すると、金属微粒子の使用量が、該反応溶媒を含めた全重量に対して０．１〜５０重量％となるようにすることが好ましい。
【００７２】
前記反応溶媒としては、水以外の溶媒、すなわち、非水溶媒が好ましい。非水溶媒の具体例としては、本発明の第１の製造方法において例示したものと同様である。
前記反応溶媒の好ましい具体例としては、本発明の第１の製造方法において組み合わせＢの場合に好ましい反応溶媒として例示したものと同様である。
金属硫化物を生成させる際には、前記混合系に含まれる水分は少ない方が、得られる金属硫化物の欠陥が少なくなるため好ましい。具体的には、組み合わせＣを原料とする場合には、前記混合系中の水分／金属微粒子中の金属原子（モル比）が４未満のわずかな水分しか含有しないことが好ましく、前記モル比が１未満であるとさらに好ましく、０．５未満であると特に好ましい。一方、組み合わせＤを原料とする場合には、前記混合系中の水分／金属微粒子中の金属原子（モル比）が１未満のわずかな水分しか含有しないことが好ましく、前記モル比が０．２未満であるとさらに好ましく、０．１未満であると特に好ましい。
【００７３】
本発明の第３の製造方法において、前記混合系を高温状態にするとは、前記混合系の温度を常温よりも高い温度（金属硫化物が生成する温度）にまで昇温することである。高温状態の温度（金属硫化物が生成する温度）は、得ようとする金属硫化物の種類等によって異なるが、通常５０℃以上であり、結晶性の高い金属硫化物を得るためには、１００℃以上が好ましく、さらに１００〜３００℃の範囲であるのが好ましい。特に、後述するように金属硫化物を膜として得ようとする場合であって基材として高分子フィルム等の有機物の基材を用いる場合には、１００〜２００℃の範囲であるのが好ましく、より好ましくは１００〜１５０℃の範囲である。
【００７４】
前記混合系を高温状態にする際の具体的な昇温手段（予備反応物を得る場合に緩やかな高温状態にする際の昇温手段も含む）としては、ヒーター、温風や熱風による加熱が一般的であるが、これに制限されるものではなく、例えば、紫外線照射などの手段を採用することもできる。加熱により高温状態にする場合は、常圧下、加圧下、減圧下のいずれの圧力下で行ってもよく、特に限定はされないが、反応溶媒等の沸点が金属硫化物の生成する温度よりも低い場合は、耐圧反応装置を用いて行うことも好ましい。通常、反応温度、反応時の気相圧は、溶媒となる成分の臨界点以下で行うが、超臨界条件で行うこともできる。
【００７５】
本発明の第３の製造方法においては、前記高温状態において前記混合系に塩基性物質を存在させるようにすることが好ましい。これにより、金属硫化物をより低温で生成させることができる。
前記塩基性物質の具体例および好ましい例としては、本発明の第２の製造方法における塩基性物質として前述したものと同様のものが挙げられる。なお、塩基性物質は、１種のみを用いてもよいし、２種以上を併用してもよい。
前記塩基性物質の使用量については、特に限定はないが、金属微粒子の金属原子の総モル数に対して、０．０１〜５倍モルとするのが好ましく、０．０５〜２倍モルとするのがより好ましい。
【００７６】
本発明の第３の製造方法において、前記混合系（前記金属微粒子とチオール化合物との混合物および／または前記金属微粒子とチオール化合物との予備反応物）を得る際の混合と、前記混合系を高温状態にする際の昇温（予備反応物を各原料の混合と、さらに緩やかな高温状態にすることとで得る場合において、緩やかな高温状態にする際の昇温も含む）とは、別々に行っても、同時（一部同時も含む）に行ってもよく、特に限定はされない。具体的には、例えば、１）金属微粒子とチオール化合物、および必要に応じて反応溶媒を混合した後、該混合物を所定温度に昇温する、２）チオール化合物を所定温度に昇温しておき、該温度を維持しながら、これに金属微粒子を混合する（この場合、反応溶媒は、チオール化合物とともに昇温してもよいし、金属微粒子とともに混合してもよい）、３）反応溶媒と金属微粒子を混合して所定温度に昇温しておき、該温度を維持しながら、これにチオール化合物を混合する、４）金属微粒子とチオール化合物、および必要に応じて反応溶媒を別々に所定温度に昇温しておいた後、これらを混合する、等が好ましく挙げられる。
【００７７】
以上の本発明の第１から第３の製造方法において、前記出発原料に２種以上の金属成分が含まれる場合、２種以上の金属元素を含む金属硫化物、例えば、複合金属硫化物、固溶体金属硫化物、あるいは２種以上の金属硫化物の混合物を得ることができる。
前記複合金属硫化物とは、金属組成比に応じて、その結晶構造（Ｘ線回析パターンまたは電子線回析パターン）が、各金属の単一金属硫化物と実質的に異なるものを意味する。
前記固溶体金属硫化物とは、その結晶構造（Ｘ線回析パターンまたは電子線回析パターン）は主たる金属成分の金属硫化物（母体）に帰属し、前記主たる金属成分以外の金属成分（ドーパント金属）が、主成分金属の一部と置換する形態（置換型固溶体）、もしくは、結晶格子内の隙間に存在する形態（侵入型固溶体）のいずれかの形態で、母体の金属硫化物中に含有されるものである。母体の金属硫化物としては、単一金属の硫化物であってもよいし、複合金属硫化物であってもよい。固溶体金属硫化物におけるドーパント金属の含有量は、通常、主成分金属に対して０．０１〜３０原子％の範囲である。
【００７８】
前記固溶体金属硫化物は、光吸収特性、発光特性、電気伝導特性、磁気特性などの各種特性を制御するのに有効である。例えば、ドーパント金属として、Ｍｎ、Ｓｂ、希土類金属などの発光金属イオンを好ましくは０．１〜１％固溶させた金属硫化物は、発光（蛍光）特性を示す発光体として有用であり、ドーパント金属として、Ｃｏ、Ｆｅ、Ｎｉ、Ｍｎなどの磁性金属イオンを好ましくは１〜３０％固溶させた金属硫化物は、希薄磁性半導体特性が期待できる。なお、発光（蛍光）特性や希薄磁性半導体特性を所望する場合、母体の金属硫化物としては、可視光の透過性が高い組成のものが好ましく、例えば、Ｚｎ、Ｙなどの金属の硫化物が好適である。
【００７９】
前記複合金属硫化物を得ようとする場合、第１および第２の製造方法においては、前記出発原料のうち異なる金属元素を有する２種以上を適宜選択すればよい。第３の製造方法においては、少なくとも１種の金属微粒子と任意の金属元素含有化合物（第１および第２の製造方法における金属元素を含有する出発原料のいずれか）とを用いるようにしてもよいし、金属微粒子として合金微粒子を用いるようにしてもよいが、合金微粒子を用いるようにすると金属微粒子のみで複合金属硫化物を得ることができ、他の金属元素含有化合物の未反応物が残留する恐れがないので好ましい。金属元素含有化合物としては、前記金属ジチオカルボン酸塩や前記チオ−ｓ−カルボン酸塩が好ましい。
【００８０】
前記固溶体金属硫化物を得ようとする場合、ドーパント金属となる原料として、第１および第２の製造方法においては、第１および第２の製造方法における金属元素を含有する出発原料のいずれか（但し、金属（チオ）アルコキシ基含有化合物の場合はｍ＝０のものが好ましい。）を好ましく用いることができるが、より好ましくは採用する製造方法（出発原料の組み合わせ）において必須となる金属元素含有原料を用いるのがよい。第３の製造方法においては、任意の金属元素含有化合物（第１および第２の製造方法における金属元素を含有する出発原料のいずれか。但し、金属（チオ）アルコキシ基含有化合物の場合はｍ＝０のものが好ましい）をドーパント金属として用いるようにしてもよいし、金属微粒子として合金微粒子を用いるようにしてもよいが、合金微粒子を用いるようにすると金属微粒子のみで複合金属硫化物を得ることができ、他の金属元素含有化合物の未反応物が残留する恐れがないので好ましい。金属元素含有化合物を用いる場合は、特に、前記金属（チオ）アルコキシ基含有化合物（ｍ＝０）、前記金属ジチオカルボン酸塩、前記チオ−ｓ−カルボン酸塩が好ましい。
【００８１】
以上の本発明の第１から第３の製造方法においては、生成する金属硫化物を粒子状で得るようにしてもよいし、生成する金属硫化物を基材の表面に膜として定着させて得るようにしてもよい。
生成する金属硫化物を粒子状で得る場合、１〜１００ｎｍであることが好ましく、１〜２０ｎｍであることがより好ましい。平均粒子径が１ｎｍ未満であると、金属硫化物に期待される各種の特性（特に発光特性）が得られにくくなり、一方、１００ｎｍを越えると、該粒子の分散液の分散安定性が不充分となり、成膜性等が悪化しやすくなる。
【００８２】
前記各製造方法において、金属硫化物は、前記混合系を高温状態にすることで得られる反応液（分散液）中に粒子として生成する。詳しくは、本発明の各製造方法によれば、前記平均粒子径に制御された金属硫化物粒子が、０．１〜５０重量％、好ましくは１〜２０重量％で分散した反応液（分散液）が得られる。したがって、粒子（粉末）として金属硫化物を得ようとする場合には、得られた前記反応液（分散液）を遠心分離や濾過などの通常の分離手段に供するようにすればよい。また、得られた前記反応液（分散液）を、限外濾過膜を用いるか、加熱によって溶媒の一部を除去することにより所望の濃度の濃縮液として用いたり、ペースト状に加工して用いることもできる。さらに、得られた前記反応液（分散液）、前記濃縮液もしくはペースト状加工物を所望の溶媒の共存下で加熱するなどして、前記反応液（分散液）、前記濃縮液もしくはペースト状加工物に始めに含まれる溶媒を除去し、所望の溶媒に置き換えるようにしてもよい。このような反応液（分散液）、濃縮液もしくはペースト状加工物は、そのままもしくは必要に応じてバインダー成分等を混合するなどして、金属硫化物膜の膜形成材料や塗料として好適に用いることができる。
【００８３】
生成する金属硫化物を基材の表面に膜として定着させて得る場合、前記混合系を基材に接触させ、この接触系を高温状態にすることにより、金属硫化物を生成させるようにする方法（以下、「方法Ｉ」とする）、前記混合系を高温状態にしながらか、または、高温状態にしておいて前記基材の表面に塗布するようにする方法（以下、「方法ＩＩ」とする）、などによって容易に得ることができる。前記方法Ｉによる場合、さらに詳しくは、前記接触系を高温状態にすることを、前記混合系を前記基材の表面に塗布しておいて前記基材を高温状態にする方法（以下、「方法Ｉ−１」とする）、前記基材を前記混合系に漬けておいて高温状態にする方法（以下、「方法Ｉ−２」とする）のいずれかで行うようにすればよい。方法Ｉ−１と方法ＩＩとは、前記混合系を基材の表面に塗布する方法であり、方法Ｉ−１では塗布後に、方法ＩＩでは塗布前もしくは塗布中に、混合系を高温状態にすることにより、基材の表面に金属硫化物を定着させ金属硫化物層を形成させる方法である。一方、方法Ｉ−２は、前記混合系に基材を浸漬した状態で該混合系を高温状態にすることにより、基材の表面に金属硫化物を析出させ成長させて、基材表面に金属硫化物を定着させ金属硫化物層を形成させる方法である。以下、方法Ｉ−１と方法ＩＩとを塗布法として、方法Ｉ−２を浸漬法として、それぞれ説明する。
【００８４】
前記塗布法において、方法Ｉ−１では前記混合系の基材へ塗布後に、方法ＩＩでは前記混合系の基材へ塗布前もしくは塗布中に、混合系を高温状態にするものであり、混合系を得る際の混合、高温状態とする際の昇温、および基材への塗布のタイミングについては、特に制限はない。但し、前記混合系が予備反応物を含む場合、予備反応物は常温で長時間溶解状態で存在し難い傾向があるため、予備反応物を得たあとは、速やかに該混合系を基材に塗布することが好ましい。また、方法ＩＩと方法Ｉ−１を組み合わせる形態も好ましく、塗布前または塗布中に昇温した混合系を基材に塗布した後、さらに該基材を昇温することが好ましい。
【００８５】
方法ＩＩのうち、前記混合系の基材へ塗布中に、混合系を高温状態にする形態の具体例としては、例えば、混合系を、基材の塗布部分に直結する加熱されたパイプに通して加熱し、塗布する形態や、混合系を、ロールコーターのパン中で加熱し、加熱された状態のまま基材に塗布する形態、などが挙げられるが、特にこれらに限定はされない。方法ＩＩのうち、前記混合系の基材へ塗布前に、混合系を高温状態にする形態の具体例としては、例えば、混合系を、（耐圧）回分式反応装置などを用いて加熱しておき、基材に塗布する形態、などが挙げられるが、特に限定されるわけではない。
【００８６】
前記塗布法を採用する場合であって前記混合系に反応溶媒を含む場合には、反応溶媒として、常圧における沸点が金属硫化物の生成する温度（高温状態にする際の温度）よりも高い反応溶媒を選択することが好ましい。これにより、透明性に優れた金属硫化物層や、硫化物含有量の高い金属硫化物層が容易に得られる。また、この場合、反応溶媒の含有量は、混合系中の金属に対するモル比で、等モル以上であることが好ましく、より好ましくは２倍モル以上である。また、前記塗布法を採用する場合であって前記混合系に反応溶媒を含む場合には、反応溶媒として、水と共沸し得る非水溶媒を選択することが好ましい。これにより、緻密な金属硫化物層を、より低温で容易に形成することができる。この場合、反応溶媒の含有量は、混合系中の金属に対するモル比で、等モル以上であること好ましく、より好ましくは２倍モル以上、さらに好ましくは５倍以上である。なお、塗布法においては、加熱により、金属酸化物層が形成されるとともに、反応溶媒等を揮発させ除去させることができる。
【００８７】
前記塗布法において、混合系を基材に塗布する際の方法としては、特に制限はなく、具体的には、例えば、バーコーター法、ロールコーター法、ナイフコーター法、ダイコーター法、スピンコート法、ディッピング法などの従来公知の方法を採用すればよい。
前記塗布法において、高温状態とする際には、基材のみを昇温してもよいし、塗布面のみを昇温するようにしてもよいし、基材および塗布面の両方を昇温してもよく、特に限定はされない。
前記塗布法において、方法ＩＩと方法Ｉ−１を組み合わせる形態を採用する場合、塗布前または塗布中に高温状態とする際の温度は、予備反応物を生成させる程度の温度が好ましく、具体的には、５０℃以上でかつ塗布後に高温状態とする際の温度以下であることが好ましい。
【００８８】
前記塗布法においては、高温状態にする際の加熱時間は、特に限定されるわけではなく、具体的には、１０秒〜１時間が好ましいが、結晶性を高めたり基材との密着性を高めるなどといった目的で、さらに加熱して熟成させてもよい。熟成の際の温度や時間、昇温手段については、特に限定はなく、適宜選択すればよい。
前記塗布法は、連続層、特に、表面の平滑性が高くかつ緻密な連続層の金属硫化物層を得る場合に好適である。
前記浸漬法においては、金属硫化物の生成が完全に終わるまでに、好ましくは金属硫化物の生成反応を開始させるまでに、基材を前記混合系に漬けておけばよく、混合系を得る際の混合、高温状態とする際の昇温、および基材の浸漬のタイミングについては、特に制限はない。但し、前記混合系が予備反応物を含む場合、予備反応物は常温で長時間溶解状態で存在し難い傾向があるため、予備反応物を得たあとは、速やかに該混合系に基材を浸漬することが好ましい。
【００８９】
前記浸漬法においては、通常用いられている装置を使用することができるが、基材を固定する機能を備えたものが好ましい。例えば、基板（基材）ホルダーを設置してなる回分式反応装置を使用することができる。撹拌の有無や、撹拌条件は特に限定されず、適宜選択すればよい。
前記浸漬法において、高温状態にする際には、基材を漬けている状態で混合系全体を昇温するようにしてもよいし、基材を漬けている状態で基材のみを選択的に昇温するようにしてもよいが、基材のみを選択的に昇温する方が、基材表面での反応が選択的に起こりやすく、基材表面に密着性の高い金属硫化物層が形成されやすいため好ましい。
【００９０】
前記浸漬法は、不連続層や多孔質構造を有する連続層の金属硫化物層を得る場合に好適である。但し、高温状態にする際の温度や原料の種類によって、金属硫化物層のマクロな構造（連続層か不連続層か、または、緻密性に優れているか多孔質であるか、など）や、結晶構造（結晶子の大きさや形状など）を制御することができる。
生成する金属硫化物を基材の表面に膜として定着させて得る際の基材としては、その材質は、特に限定されるわけではなく、具体的には、例えば、酸化物、窒化物、炭化物などのセラミックス、ガラス等の無機物；ＰＥＴ、ＰＢＴ、ＰＥＮなどのポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンサルファイド樹脂、ポリエーテルサルフォン樹脂、ポリエーテルイミド樹脂、ポリイミド樹脂、アモルファスポリオレフィン樹脂、ポリアリレート樹脂、アラミド樹脂、ポリエーテルエーテルケトン樹脂、（メタ）アクリル樹脂、ＰＶＣ樹脂、ＰＶＤＣ樹脂、ＰＶＡ樹脂、ＥＶＯＨ樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ＰＴＦＥ、ＰＶＦ、ＰＧＦ、ＥＴＦＥなどのフッ素樹脂、エポキシ樹脂、ポリオレフィン樹脂等の各種樹脂や、これら各種樹脂にアルミ、アルミナ、シリカなどを蒸着した加工品等の有機物；各種金属類；等が好ましく挙げられる。また、その形態は、具体的には、例えば、フィルム状、シート状、板状、繊維状、積層体状などが挙げられるが、特に限定はされない。また、前記基材は、機能的には、特に限定はされず、具体的には、光学的には透明、不透明；電気的には絶縁体、導電体、ｐ型またはｎ型の半導体あるいは誘電体；磁気的には磁性体、非磁性体；など目的に応じて選択される。
【００９１】
本発明の第１から第３の製造方法において、生成する金属硫化物を基材の表面に膜として定着させて得る場合であって、得られた金属硫化物が有機基を有する場合には、さらに以下のような処理をすることにより、該金属硫化物層が有する有機基を除去するようにしてもよい。すなわち、気相中（空気中などの酸化性雰囲気下、還元性雰囲気下、不活性雰囲気下など）での加熱により有機基を分解する処理、液相中での加熱により有機基を分解する処理、酸性または塩基性の水溶液を用いて化学的方法により分解する処理、有機基がカルボキシル基の場合はアルコール存在下での加熱処理、有機基がアルコキシ基の場合は酢酸存在下での加熱処理、有機鎖の切断に有効な波長３００ｎｍ以下（特に、波長２００ｎｍ以下）の紫外線による高エネルギー紫外線照射処理、コロナ放電による処理などである。なお、前記高エネルギー紫外線照射処理を施す場合は、高圧水銀ランプよりも短波長（高エネルギー）の紫外線を多く含む低圧水銀ランプを用いることが好ましい。
【００９２】
生成する金属硫化物を基材の表面に膜として定着させて得る場合、金属硫化物層の厚み（基材の表面に対して垂直な方向の厚み）は、特に限定はされないが、通常、１ｎｍ〜１０００μｍであることが好ましく、より好ましくは１ｎｍ〜１０μｍである。
本発明の第１から第３の製造方法により得られる金属硫化物（粒子または膜）は、優れた導電機能、光伝導機能、発光機能、磁気機能、光磁気機能などを有するものであり、例えば、各種表示素子のＬＥＤ膜、蛍光体膜、導電膜、記録・記憶素子の（希薄）磁性半導体膜、強磁性膜などとして好適に用いることができる。
【００９３】
【実施例】
以下に、実施例により、本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下では、便宜上、「重量部」を単に「部」と記すことがある。
＜金属硫化物粒子の製造＞
下記実施例で得られた粒子の分散液の分析は、以下のようにして行った。
（粉末試料の作製） 分散液中の粒子を遠心分離操作によって分離した後、アセトンにて洗浄し、その後６０℃で２４時間真空乾燥して揮発成分を完全に除去して微粒子の粉末を得、これを粉末試料とした。
【００９４】
（粒子の結晶構造および同定） 粉末試料の粉末Ｘ線回析測定、もしくは試料台に展開させた分散液を試料として電界放射型透過型電子顕微鏡観察および電子線回析測定を行うことにより、粒子の結晶構造を判定した。さらに、試料台に展開させた分散液を試料として電界放射型透過型電子顕微鏡で観察しながら、最高分解能１ｎｍφでスポットを絞り込めるＸＭＡを用いて元素分析を行うことにより、金属種を同定するとともに、硫黄原子／金属原子の比率を定量して組成を決定した。
（平均粒子径） 分散液を試料として電界放射型透過型電子顕微鏡により測定した。但し、電界放射型透過型電子顕微鏡によって測定し難い場合には、次のようにして測定した結晶子径（Ｄｗ）もしくは比表面積径（Ｄｓ）を平均粒子径とした。すなわち、結晶子径（Ｄｗ）は、粉末試料の粉末Ｘ線回析測定を行い、Ｗｉｌｓｏｎ法により求めた。粉末試料の粉末Ｘ線回析測定において非晶質であった粒子については、Ｂ．Ｅ．Ｔ．法により比表面積および真比重を測定し、下記式より比表面積径（Ｄｓ）を求めた。
【００９５】
Ｄｓ＝６０００／（ρ・Ｓ）
Ｄｓ：比表面積径［ｎｍ］、ρ：真比重、Ｓ：比表面積［ｍ²／ｇ］
（分散液中の粒子濃度） 分散液中の粒子を遠心分離操作によって分離した後、アセトンにて洗浄し、その後６０℃で２４時間真空乾燥して得られた残分量を粒子量として、分散液中の粒子濃度を算出した。
（金属の含有比） 粒子が２種以上の金属成分を含むと考えられる場合には、粉末試料の蛍光Ｘ線分析を行い、各金属の含有量を定量して、各金属の含有比を算出した。
【００９６】
（参考例−亜鉛ビス（チオ−ｓ−酢酸）の合成）
後述する実施例１Ａ−１と同様の反応装置を用い、反応器内に、酢酸亜鉛無水物１０部とチオ−ｓ−酢酸２００部とを仕込み、反応器内の気相部を窒素ガスでパージした後、攪拌しながら昇温し、加圧下、１５０℃で１０時間加熱した。このとき、加熱中に遊離・生成した酢酸は、適宜反応系から留去させた。加熱終了後、得られた反応液をエバポレータで加熱濃縮し、生成した沈殿物を濾過して、チオ−ｓ−酢酸で洗浄した後、真空乾燥することにより、亜鉛ビス（チオ−ｓ−酢酸）を得た。
【００９７】
なお、以下の実施例における他の金属チオ−ｓ−カルボン酸塩および金属ジチオカルボン酸塩についても、該参考例と同様の方法で合成した。
（実施例１Ａ−１）
攪拌機、添加口、温度計、留出ガス出口、窒素ガス導入口を備えた、外部より加熱し得る耐圧ガラス製反応器（容量１リットル）、および、添加口にボールバルブを介して直結する添加槽、留出ガス出口に圧力弁（２ＭＰａに設定）を介して直結する水酸化ナトリウム水溶液を充填したトラップ（反応で生成したガスにより反応器内の圧力が２ＭＰａを超えると、ガスは系内から留去されて該トラップに捕集されることになる）を備えた耐圧回分式反応装置を用意した。
【００９８】
前記反応器内に、原料Ｉ（Ａ１成分）として亜鉛ビス（チオ−ｓ−酢酸）３０部と、原料ＩＩ（Ａ２成分）としてｎ−ヘキサンチオール３２８部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１５０℃に昇温した。加圧下、１５０℃±２℃で１時間保持した後、常温（２０℃）まで冷却して、粒子の分散液３５０部を得た。
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が１０ｎｍの単結晶からなるＺｎＳ粒子であり、分散液中の粒子濃度は３．８重量％であった。
【００９９】
（実施例１Ａ−２〜１Ａ−１２）
実施例１Ａ−１と同様の反応装置を用い、原料Ｉと原料ＩＩの種類および量、昇温時の温度を表１に示すように変更し、さらに原料Ｉ、ＩＩとともに表１に示す溶媒を反応器に仕込むようにしたこと、および昇温する際の加熱温度を表１に示すように変更したこと以外は、実施例１Ａ−１と同様にして、分散液を得た。得られた分散液の得量、および該分散液の分析結果を表２に示す。なお、実施例１Ａ−１についても表１、表２に併せて示す。
なお、表１においては、下記の略号を用いた。
ＰＧＭＡＣ：プロピレングリコールメチルエーテルアセテート
ＥＧＥＡＣ：エチレングリコールエチルエーテルアセテート
ＭＢＡ：３−メトキシブチルアセテート
ＤＢＥ：ジベンジルエーテル
ＭＩＢＫ：メチルイソブチルケトン
ＢＡ：酢酸ブチル
ＴＯＬ：トルエン
ＰＧＤＭ：プロピレングリコールジメチルエーテル
【０１００】
【表１】

【０１０１】
【表２】

【０１０２】
（実施例１Ａ−１３）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（Ｂ１成分）として銅（II）エトキシド１５部と、原料ＩＩ（Ｂ２成分）としてチオ−ｓ−酢酸７４部と、溶媒としてプロピレングリコールメチルエーテルアセテート２５０部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１８０℃に昇温した。加圧下、１８０℃±２℃で１時間保持した後、常温（２０℃）まで冷却して、粒子の分散液３２９部を得た。
【０１０３】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が８ｎｍの単結晶からなるＣｕＳ粒子であり、分散液中の粒子濃度は２．８重量％であった。
（実施例１Ａ−１４）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（Ｂ１成分）として銅（I）チオフェノキシド（和光純薬製）２０部と、原料ＩＩ（Ｂ２成分）としてヘキサンジチオ酸３４部と、溶媒として３−メトキシブチルアセテート３００部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１５０℃に昇温した。加圧下、１５０℃±２℃で１時間保持した後、常温（２０℃）まで冷却して、粒子の分散液３６０部を得た。
【０１０４】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が３ｎｍの単結晶からなるＣｕ₂Ｓ粒子であり、分散液中の粒子濃度は２．６重量％であった。
（実施例１Ａ−１５）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（Ｂ１成分）として銅（II）ジメチルアミノエトキシド２０部と、原料ＩＩ（Ｂ２成分）としてｐ−［メトキシ（チオカルボニル）］ジチオ安息香酸４６部と、溶媒としてエチレングリコールエチルエーテルアセテート２５０部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１５０℃に昇温した。加圧下、１５０℃±２℃で１時間保持した後、常温（２０℃）まで冷却して、粒子の分散液３５０部を得た。
【０１０５】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が１５ｎｍの単結晶からなるＣｕＳ粒子であり、分散液中の粒子濃度は２．５重量％であった。
（実施例１Ｂ−１）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属カルボン酸塩）として酢酸パラジウム（II）２２部と、原料ＩＩ（アルコール）としてメタノール５００部と、原料ＩＩＩ（還元性物質）としてモノエタノールアミン１４部と、原料ＩＶ（チオール化合物）として１，４−ブタンジチオール２４部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１５０℃に昇温した。加圧下、１５０℃±２℃で１０分間保持した後、常温（２０℃）まで冷却して、粒子の分散液５６５部を得た。
【０１０６】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が８ｎｍの単結晶からなるＰｄＳ粒子であり、分散液中の粒子濃度は２．４重量％であった。
（実施例１Ｂ−２）
実施例１Ａ−１と同様の反応装置を用い、添加槽に、原料Ｉ（チオール化合物）として２−ジブチルアミノ−４，６−ジメルカプト−Ｓ−トリアジン（ジブチルトリアジンジチオール）２８部と２−ブトキシエタノール１００部とからなる混合溶液を仕込み、添加槽内の気相部を窒素ガスでパージした後、窒素ガスで０．２ＭＰａに加圧しておいた。一方、反応器内に、原料ＩＩ（金属カルボン酸塩）として酢酸銅（II）１８部と、原料ＩＩＩ（アルコール）として２−ブトキシエタノール４００部と、原料ＩＶ（還元性物質）としてモノエタノールアミン１５部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１５０℃に昇温した。昇温中、反応器内の液がワインレッドに変色した時点で、添加槽内の混合溶液を１分間かけて反応器内に添加した。その後、加圧下、１５０℃±２℃で１０分間保持した後、常温（２０℃）まで冷却して、粒子の分散液５６０部を得た。
【０１０７】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が５ｎｍの単結晶からなるＣｕ₂Ｓ粒子であり、分散液中の粒子濃度は１．４重量％であった。
（実施例１Ｂ−３）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属アルコキシ基含有化合物）として銅（II）メトキシエトキシエトキシド２５重量％含有メトキシエトキシエタノール１００部と、原料ＩＩ（カルボキシル基含有化合物）として酢酸１２部と、原料ＩＩＩ（還元性物質）としてｎ−ブチルアミン３０部と、原料ＩＶ（チオール化合物）としてチオフェノール２７部と、溶媒としてメタノール４５０部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１７０℃に昇温した。加圧下、１７０℃±２℃で１０分間保持した後、常温（２０℃）まで冷却して、粒子の分散液６１５部を得た。
【０１０８】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が５ｎｍの単結晶からなるＣｕ₂Ｓ粒子であり、分散液中の粒子濃度は１．０重量％であった。
（実施例１Ｃ−１）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属微粒子）としてニッケル（Ｎｉ）微粒子６部と、溶媒としてエチレングリコールモノエチルエーテル４００部と、原料ＩＩ（チオール化合物）として２−ジブチルアミノ−４，６−ジメルカプト−Ｓ−トリアジン３０部と、塩基性化合物としてシクロヘキシルアミン１９部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて２００℃に昇温した。加圧下、２００℃±２℃で５時間保持した後、常温（２０℃）まで冷却して、粒子の分散液４３４部を得た。
【０１０９】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が１５ｎｍの単結晶からなるＮｉＳ粒子であり、分散液中の粒子濃度は２．０重量％であった。
（実施例１Ｃ−２）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属微粒子）として銅（Ｃｕ）微粒子６部と、溶媒としてプロピレングリコールモノ−ｔ−ブチルエーテル２００部と、原料ＩＩ（チオール化合物）としてフェニルメタンチオール３６部と、塩基性化合物としてジエタノールアミン１部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて２００℃に昇温した。加圧下、２００℃±２℃で５時間保持した後、常温（２０℃）まで冷却して、粒子の分散液２４０部を得た。
【０１１０】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が６ｎｍの単結晶からなるＣｕ₂Ｓ粒子であり、分散液中の粒子濃度は３．０重量％であった。
（実施例１Ｃ−３）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属微粒子）として銀（Ａｇ）微粒子１０部と、溶媒としてジプロピレングリコールモノエチルエーテル３００部と、原料ＩＩ（チオール化合物）としてシクロペンタンチオール４８部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１６０℃に昇温した。加圧下、１６０℃±２℃で５時間保持した後、常温（２０℃）まで冷却して、粒子の分散液３５５部を得た。
【０１１１】
得られた分散液中の粒子を分析したところ、該粒子は、平均粒子径が１２ｎｍの単結晶からなるＡｇ₂Ｓ粒子であり、分散液中の粒子濃度は３．０重量％であった。
＜金属硫化物膜の製造＞
下記実施例で得られた膜の分析は、以下のようにして行った。
（膜の結晶構造および同定） 電子線回析測定もしくは薄膜Ｘ線回析測定により格子定数の値、回析パターンから結晶構造を判定した。さらに、ＥＳＣＡ測定により膜表層およびエッチング処理を行った後の内部層の元素分析を行うことにより、金属種を同定した。なお、ガラス板に付着したままで測定を充分に行うことができない場合は、ガラス板から膜を剥離して、測定を行った。
【０１１２】
（膜厚） 膜が付着したガラス板をガラスカッターで垂直に切断し、その切断面をＳＥＭにて観察し、ＳＥＭ像によって膜厚を測定した。
（実施例２Ａ−１）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（Ａ１成分）として亜鉛ビス（チオ−ｓ−酢酸）３０部と、原料ＩＩ（Ａ２成分）としてｎ−ヘキサンチオール６６部と、溶媒としてプロピレングリコール−ｔ−ブチルエーテルアセテート３００部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、１５分間かけて１００℃に昇温した。加圧下（０．２ＭＰａ）、１００℃±２℃で１０分間保持した後、常温（２０℃）まで冷却して、塗布液を得た。
【０１１３】
次に、得られた塗布液をガラス板にバーコーターで塗布した後、窒素雰囲気下１５０℃で２０分間加熱して、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＺｎＳ結晶からなる膜であり、膜厚は０．１μｍであった。
（実施例２Ａ−２〜２Ａ−９）
実施例１Ａ−１と同様の反応装置を用い、原料Ｉ、原料ＩＩ、溶媒の種類および量、塗布液を得る際の昇温時の温度（加熱温度）、ガラス板上塗布後の加熱温度（製膜温度）を表３に示すように変更したこと以外は、実施例２Ａ−１と同様にして、ガラス板上に付着した膜を得た。得られた膜の分析結果を表３に示す。なお、実施例２Ａ−１についても表３に併せて示す。
【０１１４】
なお、表３においては、下記の略号を用いた。
ＰＧＢＡＣ：プロピレングリコール−ｔ−ブチルエーテルアセテート
ＥＧＥＡＣ：エチレングリコールエチルエーテルアセテート
ＭＢＡ：３−メトキシブチルアセテート
ＥＧＢＡＣ：エチレングリコール−ｎ−ブチルエーテルアセテート
ＤＰＧＥＡ：ジプロピレングリコールエチルエーテルアセテート
【０１１５】
【表３】

【０１１６】
（実施例２Ａ−１０）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（Ｂ１成分）として銅（II）エトキシド１５部と、原料ＩＩ（Ｂ２成分）としてチオ−ｓ−酢酸７４部と、溶媒としてエチレングリコールエチルエーテルアセテート３００部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、１５分間かけて１００℃に昇温した。加圧下（０．１ＭＰａ）、１００℃±２℃で１０分間保持した後、常温（２０℃）まで冷却して、塗布液を得た。
【０１１７】
次に、得られた塗布液をガラス板にバーコーターで塗布した後、窒素雰囲気下１５０℃で２０分間加熱して、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＣｕＳ結晶からなる膜であり、膜厚は０．２μｍであった。
（実施例２Ａ−１１）
実施例２Ａ−１０における原料Ｉ（Ｂ１成分）として銅（I）チオフェノキシド（和光純薬製）２０部を、原料ＩＩ（Ｂ２成分）としてヘキサンジチオ酸３４部を、溶媒として３−メトキシブチルアセテート３００部を、用いるように変更したこと以外は、実施例２Ａ−１０と同様にして、ガラス板上に付着した膜を得た。
【０１１８】
得られた膜を分析したところ、該膜はＣｕ₂Ｓ結晶からなる膜であり、膜厚は０．１μｍであった。
（実施例２Ａ−１２）
実施例２Ａ−１０における原料Ｉ（Ｂ１成分）として銅（II）ジメチルアミノエトキシド２０部を、原料ＩＩ（Ｂ２成分）としてｐ−［メトキシ（チオカルボニル）］ジチオ安息香酸１１４部を、溶媒としてエチレングリコールモノエチルエーテルアセテート１００部およびジプロピレングリコールエチルエーテルアセテート１００部を、用いるように変更したこと以外は、実施例２Ａ−１０と同様にして、ガラス板上に付着した膜を得た。
【０１１９】
得られた膜を分析したところ、該膜はＣｕＳ結晶からなる膜であり、膜厚は０．０５μｍであった。
（実施例２Ａ−１３）
実施例２Ａ−１における原料Ｉ（Ａ１成分）として、亜鉛ビス（チオ−ｓ−酢酸）３０部およびコバルト（II）ビス（チオ−ｓ−酢酸）０.８８部を用いるように変更したこと以外は、実施例２Ａ−１と同様にして、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＺｎＳ結晶からなる膜であり、膜厚は０．１μｍであった。また、該膜は、Ｚｎに対して３原子％のＣｏ（II）を含有するものであった。
【０１２０】
（実施例２Ａ−１４）
実施例２Ａ−１における原料Ｉ（Ａ１成分）として、亜鉛ビス（チオ−ｓ−酢酸）３０部およびマンガン（II）ビス（チオ−ｓ−酢酸）０.８６部を用いるように変更したこと以外は、実施例２Ａ−１と同様にして、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＺｎＳ結晶からなる膜であり、膜厚は０．１μｍであった。また、該膜は、Ｚｎに対して３原子％のＭｎ（II）を含有するものであった。
【０１２１】
（実施例２Ａ−１５）
実施例２Ａ−１における原料Ｉ（Ａ１成分）として、亜鉛ビス（チオ−ｓ−酢酸）１２部およびカドミウム（II）ビス（チオ−ｓ−酢酸）１４.６部を用いるように変更したこと以外は、実施例２Ａ−１と同様にして、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＺｎ_0.5Ｃｄ_0.5Ｓ結晶からなる膜であり、膜厚は０．１μｍであった。
（実施例２Ｂ−１）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属カルボン酸塩）として酢酸パラジウム（II）１１部と、原料ＩＩ（アルコール）としてベンジルアルコール５００部と、原料ＩＩＩ（還元性物質）としてモノエタノールアミン８部と、原料ＩＶ（チオール化合物）として２−アミノ−４，６−ジメルカプト−Ｓ−トリアジン１２部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、６０分間かけて１００℃に昇温した。加圧下（０．１ＭＰａ）、１００℃±２℃で１０分間保持した後、常温（２０℃）まで冷却して、塗布液を得た。
【０１２２】
次に、得られた塗布液をガラス板にバーコーターで塗布した後、窒素雰囲気下１５０℃で２０分間加熱して、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＰｄＳ結晶からなる膜であり、膜厚は０．２μｍであった。
（実施例２Ｂ−２）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属カルボン酸塩）として酢酸銅（II）１８部と、原料ＩＩ（アルコール）としてメタノール１５０部およびエチレングリコールモノ−ｎ−ブチルエーテル５０部と、原料ＩＩＩ（還元性物質）としてモノエタノールアミン２０部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、１５分間かけて１００℃に昇温した。その後、室温（２０℃）まで冷却して紺色溶液を得た。該溶液に、原料ＩＶ（チオール化合物）として２−ジブチルアミノ−４，６−ジメルカプト−Ｓ−トリアジン２０重量％含有ＴＨＦ溶液１５０部を添加混合して、塗布液を得た。
【０１２３】
次に、得られた塗布液にガラス板をディッピングして塗布した後、窒素雰囲気下１５０℃で２０分間加熱して、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＣｕ₂Ｓ結晶からなる膜であり、膜厚は０．２μｍであった。
（実施例２Ｃ−１）
実施例１Ａ−１と同様の反応装置を用い、反応器内に、原料Ｉ（金属微粒子）として銅（Ｃｕ）微粒子６部と、溶媒としてエチレングリコールモノエチルエーテル２００部と、原料ＩＩ（チオール化合物）として２−ジブチルアミノ−４，６−ジメルカプト−Ｓ−トリアジン２７部とを仕込み、反応器内の気相部を窒素ガスでパージした後、密閉状態で攪拌しながら、２０℃より、２０分間かけて１２０℃に昇温し２時間保持した後、室温（２０℃）まで冷却し、未反応物である銅微粒子を濾過により除去し、得られた溶液に塩基性物質としてモノエタノールアミン３部を添加して、これを塗布液とした。
【０１２４】
次に、得られた塗布液をガラス板にバーコーターで塗布した後、窒素雰囲気下１５０℃で２０分間加熱して、ガラス板上に付着した膜を得た。
得られた膜を分析したところ、該膜はＣｕ₂Ｓ結晶からなる膜であり、膜厚は０．２μｍであった。
【０１２５】
【発明の効果】
本発明によれば、粒子径が制御された金属硫化物微粒子もしくは緻密な金属硫化物薄膜を優れた生産性で得ることができ、しかも各種金属に適用可能な、金属硫化物の製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a particulate or film-like metal sulfide.
[0002]
[Prior art]
Examples of a method for producing metal sulfide particles, particularly nano-order ultrafine particles, include a method in which hydrogen sulfide is passed through an aqueous solution of Cd or Zn perchlorate in the presence of hexametaphosphoric acid (see Non-Patent Document 1), ethane. A method in which sodium sulfide is added to and reacted with zinc perchlorate or cadmium perchlorate in the presence of an alkyl thiol compound such as thiol (see Non-patent Documents 2 and 3), and lead acetate in the presence of an aromatic thiol compound A method is known in which sodium sulfide is added and reacted (see Non-Patent Document 4). In these methods, hexametaphosphoric acid and thiol compounds are used as stabilizers for the resulting particles rather than reactants (raw materials that directly form metal sulfides), and sulfides react with hydrogen sulfide or sodium sulfide. It is produced by a so-called neutralization reaction between a metal salt and a metal salt. In addition, alkyl thiol compounds have been often used as surface stabilizers for metal sulfide particles.
[0003]
However, the conventional method described above has a limitation that applicable metals are limited to some metals such as Cd, Zn, and Pb. In addition, although the above-described conventional method can obtain extremely fine nano-order particles, its particle size distribution is large. For example, when it is desired to develop semiconductor characteristics (for example, light emission) having high particle size dependency. Therefore, it cannot be said that the function control by the particle diameter for the purpose of averaging the characteristics is sufficient. Further, the conventional method described above has a problem in that the concentration of the obtained particles is low, so that the productivity is low as an industrial production method, and the metal sulfide particles that are inevitably obtained are expensive.
[0004]
On the other hand, metal sulfide thin films have heretofore been obtained by applying a dispersion of metal sulfide fine particles obtained by the conventional method described above to the surface of a substrate and drying it. However, since the concentration of particles obtained by the above-described conventional method is low, there is a problem in that such a method has poor productivity and the metal sulfide thin film obtained is expensive. In addition, the compound used as a stabilizer when obtaining metal sulfide fine particles tends to prevent the formation of a dense film, and there is a problem that the characteristics of forming a film cannot be substantially utilized. Heretofore, a method for obtaining a metal sulfide thin film by directly fixing a metal sulfide on a substrate surface has not been known.
[0005]
[Non-Patent Document 1]
H.Matsumoto, H.Uchida, T.Matsunaga, K.Tanaka, T.Sakata, H.Mori, and H.Yoneyama, J.Phys.Chem., 98, (1994) 11549
[0006]
[Non-Patent Document 2]
H. Inoue, N. Ichiroku, T. Torimoto, T. Sakata, H. Mori, and H. Yoneyama, Langmuir, 10, (1994) 4517
[0007]
[Non-Patent Document 3]
T. Torimoto, K. Maeda, J. Maenaka, and H. Yoneyama, J. Phys. Chem., 98, (1994) 13658
[0008]
[Non-Patent Document 4]
T. Torimoto, H. Uchida, T. Sakata, H. Mori, and H. Yoneyama, J. Am. Chem. Soc., 115, (1993) 1847
[0009]
[Problems to be solved by the invention]
Therefore, the problem to be solved by the present invention is the particleDiameterAn object of the present invention is to provide a method for producing a metal sulfide, which can obtain controlled metal sulfide fine particles or a dense metal sulfide thin film with excellent productivity and can be applied to various metals.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor has intensively studied the formation reaction of metal sulfide from the viewpoint of the reaction mechanism. As a result, it has been found that crystal growth can be controlled in the range of several nm to 100 nm and various metal sulfides can be obtained by reacting a specific combination of starting materials which has not been conventionally used. Furthermore, in the said reaction, it discovered that a metal sulfide could be formed as a film | membrane not only on particle | grains but on a base material. These findings have led to the completion of the present invention.
[0011]
That is, the first method for producing a metal sulfide according to the present invention comprises a metal thio-s-carboxylate and / or a metal dithiocarboxylate and a thiol compound.ThingsA metal sulfide is produced using a starting material or a metal (thio) alkoxy group-containing compound, a thio-s-carboxyl group-containing compound and / or a dithiocarboxyl group-containing compound as a starting material. .
The second method for producing a metal sulfide according to the present invention uses a metal carboxylate and an alcohol as starting materials in the presence of a reducing substance, or a metal alkoxy group-containing compound and a carboxyl group-containing compound. And a metal sulfide is produced in the presence of a thiol compound.
[0012]
The third method for producing a metal sulfide according to the present invention is characterized in that a metal sulfide is produced in the presence of a thiol compound using metal fine particles as a starting material.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, although the manufacturing method of the metal sulfide concerning this invention is demonstrated in detail, the range of this invention is not restrained by these description, The range which does not impair the meaning of this invention except the following illustrations. And can be changed as appropriate.
First, the metal sulfide formation reaction in the first to third production methods of the present invention will be described for each production method.
<First metal sulfide production method>
The first method for producing a metal sulfide according to the present invention comprises a metal thio-s-carboxylate and / or a metal dithiocarboxylate (hereinafter referred to as “A1 component”), a thiol compound and / or an alcohol (hereinafter referred to as “a1”). (Hereinafter referred to as “combination A”) or a metal (thio) alkoxy group-containing compound (hereinafter referred to as “component B1”). ) And a thio-s-carboxyl group-containing compound and / or dithiocarboxyl group-containing compound (hereinafter referred to as “B2 component”) as essential starting materials (hereinafter, these starting materials are referred to as “combination B”) .
[0014]
Specifically, as the metal thio-s-carboxylate which is the A1 component in the combination A, the oxygen atom bonded to the hydrogen atom of the carboxyl group is substituted in the molecule with a sulfur atom, and the hydrogen of the carboxyl group Any compound having at least a structure in which atoms are substituted with metal atoms may be used. Further, as the metal dithiocarboxylate which is the A1 component in the combination A, specifically, in the molecule, two oxygen atoms of the carboxyl group are substituted with sulfur atoms, and the hydrogen atom of the carboxyl group is a metal atom. Any compound having at least a structure substituted with the above-mentioned compound may be used. In addition, each metal thio-s-carboxylate and metal dithiocarboxylate may be used alone or in combination of two or more.
[0015]
The metal atom is not particularly limited, but specifically, for example, 1A group, 2A group, 3A group, 4A group, 5A group, 6A group, 7A group, 8 group, lanthanoid element, actinoid element, 1B Group, 2B group, 3B group, 4B group, 5B group, and 6B group can include metal atoms, and among these, for example, Sr, Ce, Y, Ti, V, Nb, Ta , Cr, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, Cd, Al, Ga, In, Ge, Sn, Sb and La. Metal atoms are preferred. These metal atoms may be used alone or in combination as a composite metal salt. In this specification, the periodic table uses the “periodic table of elements (1993)” published in the revised 5th edition “Chemical Handbook (edited by the Chemical Society of Japan)” (published by Maruzen Co., Ltd.) The group number is written in the sub-group system.
[0016]
Since the metal thio-s-carboxylate and the metal dithiocarboxylate are usually difficult to obtain, those synthesized from the metal carboxylate may be used. For example, it can be easily synthesized by heating a metal carboxylate in the presence of thio-s-carboxylic acid or dithiocarboxylic acid. Specifically, for example, thio-s-carboxylic acid or dithiocarboxylic acid is mixed with a metal carboxylate (preferably acetate, propionate, etc.), and an organic solvent (preferably non-polar) is used. Alcohol solvent; derivatives such as carboxylic acid ester, ketone, polyhydric alcohol and the like which do not have a hydroxyl group, compounds such as glycol diether, glycol diacetate, glycol ether acetate; aromatic hydrocarbon solvents; After heating, it can be synthesized by crystallization or concentration to dryness. In addition, it is preferable that the usage-amount of thio-s-carboxylic acid or dithiocarboxylic acid shall be 5 times mole or more with respect to metal carboxylate.
[0017]
Examples of the metal thio-s-carboxylate and the metal dithiocarboxylate include thio-s-carboxylic acid or dithiocarboxylic acid corresponding to aliphatic carboxylic acid in that metal sulfide can be generated at a lower temperature. In particular, thio-s-carboxylic acids or diacids corresponding to aliphatic carboxylic acids having 1 to 6 carbon atoms such as acetic acid, propionic acid, butanoic acid, pentanoic acid, heptanoic acid and cyclohexane acid are preferred. Those synthesized using thiocarboxylic acid are preferred. Further, in view of the fact that a metal sulfide with few reaction by-products can be easily obtained, those synthesized using thio-s-carboxylic acid or dithiocarboxylic acid corresponding to acetic acid or propionic acid are preferable. The metal thio-s-carboxylate or metal dithiocarboxylate may be a hydrate containing crystal water, but is preferably an anhydride.
[0018]
Examples of the thiol compound that is the A2 component in the combination A include methanethiol, ethanethiol, n-propanethiol, i-propanethiol, t-butanethiol, n-butanethiol, n-hexanethiol, octanethiol, dodecanethiol. , Cyclohexanethiol, ethoxyethanethiol, propenethiol and other saturated or unsaturated aliphatic thiols; 1,2-ethanedithiol, 1,2-propanedithiol, 1,2-butanedithiol, 1,4-butanedithiol, 3 Dithiols such as hydroxypropane-1,2-dithiol; thioglycols such as ethylenethioglycol (2-mercaptoethanol), propylenethioglycol, 2,4-hydroxybutanethiol; benzenethiol (thiophene) ), 2-quinolinethiol, phenylmethanethiol, mercaptobenzoic acid and other aromatic thiols; 2,4,6-trimercapto-S-triazine, 2-hydroxy-4,6-dimercapto-S-triazine 2-butoxy-4,6-dimercapto-S-triazine, 2-phenoxy-4,6-dimercapto-S-triazine, 2-amino-4,6-dimercapto-S-triazine, 2-butylamino-4, 6-dimercapto-S-triazine, 2-octylamino-4,6-dimercapto-S-triazine, 2-cyclohexylamino-4,6-dimercapto-S-triazine, 2-benzylamino-4,6-dimercapto-S -Triazine, 2-dimethylamino-4,6-dimercapto-S-triazine, 2-dibutylamino- , 6-Dimercapto-S-triazine, 2-anilino-4,6-dimercapto-S-triazine, 2-diphenylamino-4,6-dimercapto-S-triazine, 2,4,6-trimercapto-S-triazine And triazine mono (di) (tri) thiols such as monosodium salt; In addition, a thiol compound may use only 1 type and may use 2 or more types together.
[0019]
Examples of the alcohol as the A2 component in the combination A include aliphatic monohydric alcohol (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.), aliphatic unsaturated monohydric alcohol (allyl alcohol). , Crotyl alcohol, propargyl alcohol, etc.), alicyclic monohydric alcohols (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohols (benzyl alcohol, cinnamyl alcohol, methylphenyl carbitol, etc.), phenols ( Ethylphenol, octylphenol, catechol, xylenol, guaiacol, p-cumylphenol, cresol, m-cresol, o-cresol, p-cresol, dodecylphenol, naphthol, nonylfe Alcohol, phenol, benzylphenol, p-methoxyethylphenol, etc.), monohydric alcohols such as heterocyclic monohydric alcohols (furfuryl alcohol, etc.); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc.), aliphatic glycol having an aromatic ring (Hydrobenzoin, benzpinacol, phthalyl alcohol, etc.), alicyclic glycols (cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, etc.), polyoxyalkylene Guri Glycols such as polyethylene glycol, polypropylene glycol, etc .; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, ethylene glycol mono Derivatives such as monoethers and monoesters of the above glycols such as ethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene glycol monoacetate; hydroquinone, resorcin, 2,2-bis (4-hydroxyphenyl) propane, etc. Aromatic diols and monoethers and monoesters thereof; trihydric alcohols such as glycerin and the like And other monoethers, monoesters, diethers, and diesters. In addition, only 1 type may be used for alcohol and it may use 2 or more types together.
[0020]
There are no particular limitations on the proportion of the A1 component (metal thio-s-carboxylate and / or metal dithiocarboxylate) and the A2 component (thiol compound and / or alcohol) in combination A, The molar ratio (thio-s-carboxyl group + dithiocarboxyl group / thiol group + hydroxyl group) of the total number of thiol groups and hydroxyl groups in the A2 component to the total number of thio-s-carboxyl groups and dithiocarboxyl groups possessed by the A1 component is 1. /0.8 to 1/1000 is preferable, and 1/1 to 1/100 is more preferable.
[0021]
Although it does not specifically limit as a metal (thio) alkoxy group containing compound which is B1 component in the combination B, For example, following General formula (1):
M (XR^a)_nmR^b _m    (1)
Wherein M is a metal atom; X is an oxygen atom or a sulfur atom; R^aIs at least one selected from a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, an aralkyl group, and an aryl group; R^bIs a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, an aralkyl group, an aryl group, an unsaturated aliphatic residue, and OR^aAt least one selected from organic groups containing a functional group other than the group; n is the valence of the metal atom M ′; m is an integer in the range of 0 to n−1. )
Or a condensate obtained by subjecting this compound to (partial) hydrolysis / condensation. In addition, a metal (thio) alkoxy group containing compound may use only 1 type, and may use 2 or more types together.
[0022]
In general formula (1), R^aIs preferably an optionally substituted alkyl group such as a hydrogen atom and / or an alkoxyalkyl group, and more preferably an optionally substituted alkyl group. R^bAs an optionally substituted alkyl group, cycloalkyl group, acyl group, aralkyl group, aryl group, unsaturated aliphatic residue, and OR such as a β-diketone compound.^aWhat is at least 1 sort (s) chosen from the organic group containing functional groups other than group is preferable.
In the general formula (1), examples of M include the same metal atoms as those of the metal thio-s-carboxylate and / or metal dithiocarboxylate in the combination A, and the same applies to preferable ones. However, W, Mo, and Si are also preferable.
[0023]
In the general formula (1), specific examples of the metal alkoxy group-containing compound in which X is an oxygen atom and m = 0 include, for example, those similar to the metal alkoxy group-containing compound in the combination D described later.
In the general formula (1), as specific examples of the metal alkoxy group-containing compound in which X is an oxygen atom and m = 1, 2 or 3, for example, various organosilicon compounds (m = 1, 2 or 3) , Titanate coupling agents (m = 1, 2 or 3), aluminate coupling agents (m = 1 or 2), and the like.
Examples of the organosilicon compound include vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and vinyltriacetoxysilane; N- (2-aminoethyl)- Amino-based silane coupling agents such as 3-aminopropylmethyldimethoxysilane, 3-N-phenyl-γ-aminopropyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; Epoxy silane coupling agents such as glycidoxypropyltrimethoxysilane and β- (3,4-eboxycyclohexyl) ethyltrimethoxysilane; Chlorine silane coupling agents such as 3-chloropropyltrimethoxysilane; Roxypropyltrimethoxy Methacryloxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine Ketimine-based silane coupling agents such as: Cationic silane coupling agents such as N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride; methyltrimethoxysilane, trimethylmethoxysilane, Examples thereof include alkyl silane coupling agents such as decyltriethoxysilane and hydroxyethyltrimethoxysilane; γ-ureidopropyltriethoxysilane.
[0024]
Examples of the titanate coupling agent include isopropyl triisostearoyl titanate, isopropyl trioctaloyl titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl tris (dioctyl pyrone). Phosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl (N-aminoethyl-aminoethyl) titanate, tetra (2,2- Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyldimethac Louis isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, and can include isopropyl tricumylphenyl titanate.
[0025]
Examples of the aluminate coupling agent include diisopropoxyaluminum ethyl acetoacetate, diisopropoxyaluminum alkyl acetoacetate, diisopropoxyaluminum monomethacrylate, isopropoxyaluminum alkyl acetoacetate mono (dioctyl phosphate), and cyclic An aluminum oxide isopropylate etc. can be mentioned. In general formula (1), since a metal thioalkoxy group-containing compound in which X is a sulfur atom is usually difficult to obtain, in general formula (1) described above, X is an oxygen atom, and m = 0. What is synthesized from a certain metal alkoxy group-containing compound may be used. For example, it can be easily synthesized by heating the metal alkoxy group-containing compound in the presence of thiol. Specifically, for example, the compound can be synthesized by mixing thiol with the metal alkoxy group-containing compound, adding an organic solvent as necessary, heating, and then crystallizing or concentrating to dryness. In addition, it is preferable that the usage-amount of thiol shall be 5 times mole or more with respect to the said metal alkoxy group containing compound.
[0026]
The metal (thio) alkoxy group-containing compound may be other than those described above, and in addition to a single metal (thio) alkoxy group-containing compound, for example, a heterometal (thio) alkoxy group such as barium titanium double alkoxide It may be a compound. In addition, a hetero metal (thio) alkoxy group-containing compound is a metal (thio) having two or more different metal atoms and connected via a (thio) alkoxy group or an oxygen atom or by a metal-metal bond or the like. An alkoxy group-containing compound. When a heterometal (thio) alkoxy group-containing compound is used, a metal sulfide composed of a composite metal sulfide can be obtained.
[0027]
In the case of obtaining a crystalline metal sulfide, it is most preferable to use a compound in which m is 0 in the general formula (1) as a main component, and a single metal (thio) alkoxy group-containing compound or heterometal ( Thio) alkoxy group-containing compounds are preferred. Moreover, when obtaining the metal sulfide by which the organic group was introduce | transduced, it is preferable to use the compound whose m is 1-n-1 as a said component at least in General formula (1).
Specifically, the thio-s-carboxyl group-containing compound which is the B2 component in the combination B is a compound having at least a structure in which an oxygen atom bonded to a hydrogen atom of the carboxyl group is substituted with a sulfur atom in the molecule. I just need it. In addition, the dithiocarboxyl group-containing compound that is the B2 component in the combination B may be a compound having at least a structure in which two oxygen atoms of the carboxyl group are substituted with sulfur atoms in the molecule. In addition, only 1 type may be used for a thio-s-carboxyl group containing compound and a dithiocarboxyl group containing compound, respectively, and 2 or more types may be used together.
[0028]
The thio-s-carboxyl group-containing compound is not particularly limited as long as it is a compound having a mercaptocarbonyl group (—C (═O) —SH). For example, a carboxylic acid group of an aliphatic or aromatic carboxylic acid ( A compound in which the oxygen atom of the OH group of —C (═O) —OH) is substituted with a sulfur atom, specifically, for example, thio-s-acetic acid, thio-s-propionic acid, thio- Examples include s-butanoic acid, hexanethio-s-acid, 3- (thiocarboxy) propionic acid, p- (mercaptocarbonyl) benzoic acid, and the like. The dithiocarboxyl group-containing compound is not particularly limited as long as it is a compound having a dithiocarboxyl group (—C (═S) —SH). For example, a carboxylic acid group of an aliphatic or aromatic carboxylic acid (— C (═O) —OH) is a compound in which the oxygen atom of the carbonyl and the oxygen atom of the OH group are both substituted with a sulfur atom. Specific examples include dithioacetic acid, dithiopropionic acid, and dithiobutanoic acid. Hexanedithioic acid, hexanebis (dithioic acid), 1-piperidinecarbodithioic acid, p- (dithiocarboxy) benzoic acid, dithio-2-naphthoic acid and the like.
[0029]
There are no particular limitations on the proportion of the B1 component (metal (thio) alkoxy group-containing compound) and B2 component (thio-s-carboxyl group-containing compound and / or dithiocarboxyl group-containing compound) in combination B. Is a molar ratio of the total number of thio-s-carboxyl groups and dithiocarboxyl groups in B2 component to the total number of (thio) alkoxy groups possessed by B1 component (thio-s-carboxyl group + dithiocarboxyl group / (thio) alkoxy group) ) Is preferably 0.8 or more, and more preferably 1 or more. The upper limit of the molar ratio (thio-s-carboxyl group + dithiocarboxyl group / (thio) alkoxy group) is preferably 10 or less.
[0030]
In the first production method of the present invention, the metal sulfide is generated by bringing the mixed system of the starting materials essentially including the combination A or B into a high temperature state.
In the first production method of the present invention, the mixed system of the starting materials means a mixture obtained by mixing the starting materials and / or a preliminary reaction product obtained from the starting materials. A part of the mixed system may be a preliminary reaction product, and the other may be a mixture of the starting materials.
The pre-reacted product is an arbitrary product until a metal sulfide is generated as a reaction product obtained by reacting the A1 component and the A2 component in the combination A or a reaction product obtained by reacting the B1 and B2 components in the combination B. It is a reaction intermediate in a stage state (a state before formation of metal sulfide is observed), and is a precursor to the metal sulfide to be generated (metal sulfide precursor). That is, the preliminary reaction product is a metal sulfide precursor that is not any of the A1 component, the A2 component, the B1 component, and the B2 component, and is not a metal sulfide to be generated. Such a pre-reacted product can be obtained immediately, for example, by simply mixing the A1 component and the A2 component or the B1 component and the B2 component, or the mixture of the A1 component and the A2 component or the mixture of the B1 component and the B2 component is gently mixed. It is obtained by making it into a high temperature state (a state where the temperature is lower than the temperature at which the metal sulfide is obtained).
[0031]
The pre-reactant obtained from the starting material of the combination A is not particularly limited. For example, 1) a metal thio-s-carboxylate and / or a metal dithiocarboxylic acid may have a thiol, alcohol or (thio ) Metal complex monomers formed by coordination (including adsorption) of alkoxy groups (including complexes in which a part of thiocarboxyl group is substituted / coordinated with (thio) alkoxy group), 2) Metal thio-s- A thiol, alcohol, or (thio) alkoxy group is further coordinated (including adsorption) to a condensate obtained by condensing a carboxylate and / or a metal dithiocarboxylic acid by forming a “metal-sulfur-metal” bond via a sulfur atom. And the like are preferred. Among these, the metal complex monomer referred to in 1) is more preferable.
[0032]
The preliminary reaction product obtained from the starting material of the combination B is not particularly limited. For example, 1) a thio-s-carboxyl group-containing compound and / or dithiocarboxyl on the metal atom of the metal (thio) alkoxy group-containing compound. A metal complex monomer in which a group-containing compound is coordinated via a thiocarboxyl group or a dithiocarboxyl group (a part of the (thio) alkoxy group is substituted with a thio-s-carboxyl group or a dithiocarboxyl group. 2) a thio-s-carboxyl group-containing compound and / or a dithiocarboxyl to a condensate obtained by condensing a metal (thio) alkoxy group-containing compound by forming a “metal-sulfur-metal” bond via a sulfur atom Preferred examples include compounds formed by coordination (including adsorption) of group-containing compounds. Among these, the metal complex monomer referred to in 1) is more preferable.
[0033]
In addition, regarding the metal complex monomer which is one form of the preliminary reaction product, the coordination number is estimated to be the same as or higher than the valence of the metal atom contained, for example, the preliminary reaction product in which the metal atom is Zn. In this case, there are those in which 1 to 2 thiols, alcohols or (thio) alkoxy groups are further adsorbed or coordinated in addition to two thiocarboxyl groups or dithiocarboxyl groups.
The mixed system is preferably a fluid liquid such as a paste, suspension, or solution, and a reaction solvent may be used as a starting material if necessary. Specifically, when mixing the starting materials composed of the combination A or B, or when bringing the mixed system composed of these starting materials into a high temperature state, the reaction solvent may be further added.
[0034]
When the reaction solvent is also used, the amount used is not particularly limited. However, considering that a metal sulfide is economically obtained, the total of the A1 component in the case of the combination A and the total of the B1 component in the case of the combination B The amount used is preferably 0.1 to 50% by weight based on the total weight including the reaction solvent.
As the reaction solvent, a solvent other than water, that is, a non-aqueous solvent is preferable. Examples of the non-aqueous solvent include ethylbenzene, octane, xylenes, cyclohexane, cyclohexylbenzene, dimethylnaphthalene, styrene, solvent naphtha, decalin, decane, tetralin, dodecylbenzene, toluene, methylcyclohexane, methylcyclopentane, liquid paraffin, and the like. Hydrocarbon solvents; various halogenated hydrocarbon solvents; alcohols such as alcohols (including phenols, polyhydric alcohols and derivatives thereof having a hydroxyl group) as an A2 component; anisole, epichlorohydride Phosphorus, epoxy butane, crown ethers, diisoamyl ether, diethyl acetate, dioxane, diglycidyl ether, diphenyl ether, dibutyl ether, dibenzyl ether, dimethyl ether Ethers or acetal solvents such as ter, methyl-t-butyl ether; acetylacetone, acetaldehyde, acetophenone, acetone, isophorone, ethyl-n-butylketone, diacetone alcohol, diisobutylketone, cyclohexanone, di-n-propylketone, phorone, mesi Ketone or aldehyde solvents such as tiloxide, methyl-n-amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, methylcyclohexanone, methyl-n-heptyl ketone; diethyl adipate, triethyl acetylcitrate, ethyl acetoacetate, methyl abietic acid, benzoic acid Benzyl acid, methyl benzoate, isoamyl isovalerate, ethyl isovalerate, propyl formate, tributyl citrate, methyl cinnamate, 2-ethylhexyl acetate Cyclohexyl acetate, n-butyl acetate, benzyl acetate, methyl acetate, methyl cyclohexyl acetate, benzyl salicylate, methyl salicylate, dibutyl oxalate, diethyl tartrate, ethyl stearate, butyl stearate, dioctyl sebacate, dibutyl sebacate, carbonic acid Diphenyl, dimethyl carbonate, butyl lactate, methyl lactate, dioctyl phthalate, dimethyl phthalate, γ-butyrolactone, butyl propionate, benzyl propionate, methyl propionate, borate esters, dioctyl maleate, dimethyl malonate, isoamyl butyrate , Ester solvents such as methyl butyrate and phosphates; ethylene carbonate, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol diglycidyl acetate , Ethylene glycol dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol diacetate, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dibenzoate, diethylene glycol dimethyl ether , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol di-2-ethyl butyrate, triethylene glycol dimethyl ether, polyethylene glycol fatty acid diester, poly (oxyether) having no hydroxyl groups at both ends (Len-oxypropylene) derivatives and the like, wherein the active hydrogens of all hydroxyl groups of polyhydric alcohols are substituted with alkyl groups or acetoxy groups; carboxylic acids and their anhydrides; silicone oils, mineral oils, etc. it can.
[0035]
As the reaction solvent in the case of the combination A, an alcohol solvent is particularly preferable among the non-aqueous solvents described above, and an alcohol used as the component A2 as an essential starting material may be used as the solvent.
As the reaction solvent in the case of the combination B, among the above-mentioned nonaqueous solvents, for example, hydrocarbon solvents; halogenated hydrocarbon solvents; alcohol solvents; ether or acetal solvents; ketones or aldehyde solvents An ester solvent; a derivative compound in which the active hydrogens of all hydroxyl groups of the polyhydric alcohol are substituted with an alkyl group or an acetoxy group; a carboxylic acid and its anhydride; a silicone oil, a mineral oil;
[0036]
When producing a metal sulfide, it is preferable that the amount of water contained in the mixed system is small because defects of the resulting metal sulfide are reduced. Specifically, when the combination A is used as a starting material, it is preferable that the water content in the mixed system / the metal atom (molar ratio) in the component A1 contain only a small amount of water with a molar ratio of less than 4. Is more preferably less than 1, and particularly preferably less than 0.5. On the other hand, when the combination B is used as a starting material, it is preferable that the water content in the mixed system / the metal atom (molar ratio) in the B1 component is less than 1 and that the molar ratio is 0.1. More preferably, it is less than 2, and it is especially preferable that it is less than 0.1.
[0037]
In the first production method of the present invention, to bring the mixed system into a high temperature state is to raise the temperature of the mixed system to a temperature higher than room temperature (a temperature at which a metal sulfide is generated). The temperature in the high temperature state (temperature at which the metal sulfide is generated) varies depending on the type of metal sulfide to be obtained, but is usually 50 ° C. or higher. In order to obtain a metal sulfide with high crystallinity, 100 More preferably, the temperature is in the range of 100 to 300 ° C. In particular, when a metal sulfide is to be obtained as a film as will be described later and an organic material substrate such as a polymer film is used as the substrate, it is preferably in the range of 100 to 200 ° C. More preferably, it is the range of 100-150 degreeC.
[0038]
As specific temperature raising means for bringing the mixed system into a high temperature state (including a temperature raising means for bringing the preliminary reaction product into a moderately high temperature state), heating by a heater, warm air or hot air is possible. Although it is general, it is not limited to this, For example, means, such as ultraviolet irradiation, can also be employ | adopted. When heating to a high temperature state, it may be performed under normal pressure, under pressure, or under reduced pressure, and although not particularly limited, the boiling point of the reaction solvent or the like is lower than the temperature at which the metal sulfide is generated. In this case, it is also preferable to use a pressure resistant reactor. Usually, the reaction temperature and the gas phase pressure during the reaction are carried out below the critical point of the solvent component, but it can also be carried out under supercritical conditions.
[0039]
In the first production method of the present invention, mixing for obtaining the mixed system (the mixture of the starting materials and / or the pre-reacted material of the starting materials), and the temperature rise when the mixed system is brought to a high temperature state ( In the case where the pre-reacted product is obtained by mixing the A1 component and the A2 component or the B1 component and the B2 component with a mildly high temperature state, the temperature rise when the moderately high temperature state is obtained is also included. Or may be performed simultaneously (including partially simultaneously), and is not particularly limited. Specifically, for example, 1) each component (A1 component and A2 component or B1 component and B2 component, and reaction solvent as necessary) is mixed, and then the mixture is heated to a predetermined temperature. 2) A2 The component or B2 component is heated to a predetermined temperature, and the A1 component or B1 component is mixed with this while maintaining the temperature (in this case, the reaction solvent may be heated together with the A2 component or B2 component). 3) The reaction solvent and the A1 component or B1 component are mixed and heated to a predetermined temperature. While maintaining the temperature, the A2 is added to the reaction solvent and the A1 component or the B1 component. 4) Mix each component (A1 component and A2 component or B1 component and B2 component and, if necessary, the reaction solvent) separately at a predetermined temperature, and then mix these components Do And the like preferably.
[0040]
<Method for producing second metal sulfide>
The second method for producing a metal sulfide of the present invention uses a metal carboxylate and an alcohol as essential starting materials, or uses a metal alkoxy group-containing compound and a carboxyl group-containing compound as essential starting materials, The raw material mixing system is brought to a high temperature state, and at this time, the reducing material is added to at least one of the starting materials before mixing the starting materials, and at the same time or after the addition of the reducing materials. A thiol compound is added and the high temperature state is reached. That is, in the second method for producing a metal sulfide of the present invention, a reducing substance and a thiol compound are added to a starting material composed of a metal carboxylate and an alcohol, or a metal alkoxy group-containing compound and a carboxyl group-containing compound. The combination is the raw material, and the metal carboxylate, alcohol, reducing substance and thiol compound are essential raw materials (hereinafter these raw materials are referred to as “Combination C”), or the metal alkoxy group is contained. A compound, a carboxyl group-containing compound, a reducing substance, and a thiol compound are used as essential raw materials (hereinafter, these raw materials are referred to as “combination D”).
[0041]
Specifically, the metal carboxylate in combination C may be a compound having at least a structure in which a hydrogen atom of a carboxyl group is substituted with a metal atom in the molecule. In addition, only 1 type may be used for metal carboxylate, and 2 or more types may be used together.
The metal atom is not particularly limited, but specifically, for example, 1A group, 2A group, 3A group, 4A group, 5A group, 6A group, 7A group, 8 group, lanthanoid element, actinoid element, 1B Group, 2B group, 3B group, 4B group, 5B group, 6B group, metal atoms composed of metal elements, and among these, Pt, Pd, Ru, Rh, Ir, Fe, Co, A metal atom composed of at least one metal element selected from Ni, Cu, and Ag is preferable. These metal atoms may be used alone or in combination as a composite metal salt.
[0042]
Specific examples of the metal carboxylate include, for example, a salt composed of a chain carboxylic acid such as a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a saturated polycarboxylic acid, and an unsaturated polycarboxylic acid and the metal atom; A salt composed of a cyclic saturated carboxylic acid and the above metal atom; a salt composed of an aromatic carboxylic acid such as an aromatic monocarboxylic acid and an aromatic unsaturated polyvalent carboxylic acid and the above metal atom; And a salt comprising a compound having a functional group or atomic group such as a hydroxyl group, amino group, nitro group, alkoxy group, sulfone group, cyano group, halogen atom and the like, and the above metal atom. The metal carboxylate may be a hydrate containing crystal water, but is preferably an anhydride.
[0043]
Specific examples of the alcohol in the combination C are the same as those exemplified as the A2 component of the combination A in the first production method of the present invention. In addition, only 1 type may be used for alcohol and it may use 2 or more types together.
The ratio of the amount of metal carboxylate and alcohol used in combination C is not particularly limited, but the molar ratio of the total number of hydroxyl groups in the alcohol to the total number of carboxyl groups possessed by the metal carboxylate (carboxyl group / hydroxyl group). Is preferably 1 / 0.8 to 1/1000, and more preferably 1 / 1.2 to 1/100.
[0044]
Although it does not specifically limit as a metal alkoxy group containing compound in the combination D, For example, following General formula (2):
M (OR^a)_nmR^b _m    (2)
(However, M is a metal atom; R^aIs at least one selected from a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, an aralkyl group, and an aryl group; R^bIs a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, an aralkyl group, an aryl group, an unsaturated aliphatic residue, and OR^aAt least one selected from organic groups containing a functional group other than the group; n is the valence of the metal atom M ′; m is an integer in the range of 0 to n−1. )
Or a condensate obtained by subjecting this compound to (partial) hydrolysis / condensation. In addition, a metal alkoxy group containing compound may use only 1 type, and may use 2 or more types together.
[0045]
In general formula (2), R^aIs preferably an optionally substituted alkyl group such as a hydrogen atom and / or an alkoxyalkyl group, and more preferably an optionally substituted alkyl group. R^bAs an optionally substituted alkyl group, cycloalkyl group, acyl group, aralkyl group, aryl group, unsaturated aliphatic residue, and OR such as a β-diketone compound.^aWhat is at least 1 sort (s) chosen from the organic group containing functional groups other than group is preferable.
In the general formula (2), examples of M include the same metal atoms as those of the metal carboxylates in the combination C, and the same applies to preferable ones.
[0046]
In the general formula (2), specific examples of the metal alkoxy group-containing compound in which m = 1, 2, or 3 include, for example, various organosilicon compounds (m = 1, 2 or 3), titanate coupling agents ( m = 1, 2, or 3), aluminate coupling agents (m = 1 or 2), and the like. Specific examples of the organosilicon compound, titanate coupling agent, and aluminate coupling agent are the same as those exemplified as the B1 component of the combination B in the first production method of the present invention.
The metal alkoxy group-containing compound may be other than those described above, and may be a heterometal alkoxy group-containing compound such as a barium titanium double alkoxide in addition to a single metal alkoxy group-containing compound. The heterometal alkoxy group-containing compound is a metal alkoxy group-containing compound having two or more different metal atoms and connected via an alkoxy group or an oxygen atom, or by a metal-metal bond. When a hetero metal alkoxy group-containing compound is used, a metal sulfide composed of a composite metal sulfide can be obtained.
[0047]
In the case of obtaining a crystalline metal sulfide, it is most preferable to use a compound in which m is 0 in the general formula (2) as a main component, a single metal alkoxy group-containing compound or a heterometal alkoxy group-containing compound. Is preferred. Moreover, when obtaining the metal sulfide by which the organic group was introduce | transduced, it is preferable to use the compound whose m is 1-n-1 as a said component at least in General formula (2).
Specifically, the carboxyl group-containing compound in the combination D may be a compound having at least a carboxyl group in the molecule. In addition, only 1 type may be used for a carboxyl group-containing compound, and 2 or more types may be used together.
[0048]
Specific examples of the carboxyl group-containing compound include saturated fatty acids (saturated monocarboxylic acids) such as formic acid, acetic acid, propionic acid, isobutyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid. , Unsaturated fatty acids (unsaturated monocarboxylic acids) such as acrylic acid, methacrylic acid, crotonic acid, oleic acid, linolenic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, β, β-dimethylglutaric acid Saturated polyvalent carboxylic acids such as unsaturated carboxylic acids such as maleic acid and fumaric acid, etc .; Cyclic saturated carboxylic acids such as cyclohexane carboxylic acid; Fragrances such as benzoic acid, phenylacetic acid and toluic acid Unsaturated monocarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, etc. Aromatic carboxylic acids such as divalent carboxylic acids; carboxylic anhydrides such as acetic anhydride, maleic anhydride, pyromellitic anhydride; trifluoroacetic acid, o-chlorobenzoic acid, o-nitrobenzoic acid, anthranilic acid, p- Aminobenzoic acid, anisic acid (p-methoxybenzoic acid), toluic acid, lactic acid, salicylic acid (o-hydroxybenzoic acid) and other molecules such as hydroxyl groups other than carboxyl groups, amino groups, nitro groups, alkoxy groups, sulfonic acids A compound having a functional group or atomic group such as a group, a cyano group, or a halogen atom; (co) polymer of the above unsaturated carboxylic acid such as acrylic acid homopolymer, acrylic acid-methyl methacrylate copolymer; Can do. Of these carboxyl group-containing compounds, saturated carboxylic acid is preferable and acetic acid is most preferable in order to obtain particles having excellent dispersibility. Further, when the carboxyl group-containing compound is a liquid, it can also be used as a reaction solvent as described later.
[0049]
The ratio of the amount used of the metal alkoxy group-containing compound and the carboxyl group-containing compound in the combination D is not particularly limited, but the molar ratio of the carboxyl group-containing compound to the metal alkoxy group-containing compound is the same as the metal alkoxy group-containing compound. Using the average valence number Nav of the contained metal atom M, the lower limit is preferably more than 0.8 Nav, more preferably more than 1.2 Nav, and the upper limit is preferably less than 10 Nav. Here, the average valence number Nav is a p-type metal alkoxy group-containing compound having different metal elements as the metal alkoxy group-containing compound (p in which the metal elements are M1, M2, M3,..., Mp, respectively). When using together a kind of metal alkoxy group-containing compound (2 ≦ p)), the following formula:
[0050]
[Expression 1]

[0051]
(In the formula, Ni represents the valence (valence) of the metal Mi. Further, Xi represents the number of moles of the metal element Mi used as the metal alkoxy group-containing compound. P is an integer of 2 or more. )
It can be calculated from Further, the number of carboxyl groups contained in the total amount of the carboxyl group-containing compound is preferably more than 0.8 N ′ relative to the number N ′ of alkoxy groups contained in the total amount of the metal alkoxy group-containing compound, 1N ′ to 10N ′ are particularly preferable. In addition, when expressing a numerical range, if “super” is added after the numerical value, the numerical value range larger than that is not included.
[0052]
The reducing substances in combination C and combination D are not particularly limited, and conventionally known reducing substances can be used. Specifically, for example, formaldehyde; hydrazine compounds such as hydrazine and hydrazine derivatives; metal borohydride salts such as sodium borohydride; citric acid compounds such as citric acid and metal citrate; succinic acid and succinic acid metal salts Succinic acid compounds such as: amino group-containing compounds; compounds of low-valent metals such as Sn (II) and Mn (II); saccharides such as monosaccharides and polysaccharides; In addition to these liquid and solid substances, a reducing gas such as hydrogen gas can also be used as the reducing substance. Among these, a citric acid compound, a succinic acid compound, an amino group-containing compound, and a low-valent metal compound are preferable from the viewpoint that safety and the function of the obtained metal sulfide particles and metal sulfide film are difficult to inhibit. . Moreover, as a reducing substance, what can act also as a basic substance mentioned later (similar to the basic substance mentioned later) is preferable, and alkanolamine is particularly preferable. In addition, only 1 type may be used for a reducing substance and it may use 2 or more types together.
[0053]
Specific examples of the amino group-containing compound include a compound containing a primary to tertiary amino group and a compound containing a quaternary ammonium group. Specific examples include methylamine and isobutyl. Amine, dibutylamine, tributylamine, ethyl-n-butylamine, tert-butylamine, laurylamine, stearylamine, N-dodecyl-1-dodecanamine, N, N-dioctyl-1-octaneamine, N, N-dimethyl- 1-octadecanamine, cyclohexylamine, dicyclohexylamine and other primary, secondary or tertiary aliphatic amines, ethylenediamine, N-octadecyl-1,3-propanediamine and other aliphatic diamines, triamine, polyethyleneimine and other polyamines , Aliphatic rings such as morpholine and piperazine Aliphatic amines such as min; aliphatic or aromatic hydroxylamines such as N-phenylhydroxylamine, p- (hydroxyamino) phenol, monoethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethyl Aromatic amines such as aniline, diphenylamine, N-ethyl-N-phenylbenzylamine, o-toluidine, p-toluidine, 2,3-xylidine, o-anisidine, diaminotoluene, 4,4-methylenedianiline, phenylenediamine Tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, tetrabutylammonium hydrogen sulfate, trimethylphenylammonium bromide, tetramethylammonium bromide, tetra-n-butylammonium bromide, N Benzylpicolinium chloride, tetramethylammonium iodide, N-lauryl 4-picoronium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetramethylammonium chloride, triethylpen Quaternary ammonium salts such as zirconium; and the like. Among these, hydroxylamine is particularly preferable from the viewpoint of easily producing a metal sulfide at a low temperature.
[0054]
Specific examples of the low-valent metal compound include metal ions; hydroxides; oxides; nitrates, chlorides, carbonates (hydrogen), carboxylates, etc .; metal alkoxides; metal acetyls. Organometallic complexes such as β-diketone complexes such as acetate and β-ketoester complexes; and the like. Examples of these metal elements include Sn, Mn, V, Cr, Mo, W, Re, In, Tl, and Sb. Is mentioned.
The amount of reducing substance used in combination C and combination D is not particularly limited as long as at least an amount necessary to reduce the metal atom (cationic state) contained in the starting material to metal is present. It is preferable that the valence of the metal atom X contained in the starting material is n, and the reducing substance / metal atom X (molar ratio) is 0.5n to 5n.
[0055]
In the second production method of the present invention, the reducing substance is at least one of the starting materials before mixing the starting materials (metal carboxylate and alcohol, or metal alkoxy group-containing compound and carboxyl group-containing compound). Add to one. That is, the reducing substance is added to at least one of the two starting materials before or simultaneously with the mixing of the two starting materials. In other words, the two starting materials are mixed. In such a state, it is important to make the reducing substance coexist. Therefore, in the mixed system of the starting materials, in addition to the starting materials, the reducing material (if the mixed system is a pre-reacted material as described later, changes to a material derived from the reducing material). May be included). In the second production method of the present invention, a metal is once generated by three components of the two starting materials and the reducing material, and a metal sulfide is generated by the reaction of the metal with a thiol compound described later. Presumed to be.
[0056]
Examples of the thiol compound in the combination C and the combination D include those similar to those exemplified as the A2 component of the combination A in the first production method of the present invention. In addition, a thiol compound may use only 1 type and may use 2 or more types together.
The amount of thiol compound used in combination C and combination D is not particularly limited, and the molar ratio of the total number of thiol groups in the thiol compound to the total number of metal atoms of the metal carboxylate or metal alkoxy group-containing compound (thiol group) / Metal atom) may be equal to or greater than the molar ratio (metal sulfide S / M ratio) of sulfur atom (S) to metal atom (M) in the metal sulfide to be obtained. However, it is usually preferable that the ratio be 1 to 5 times the metal sulfide S / M ratio.
[0057]
In the second production method of the present invention, the thiol compound is mixed with the starting material (metal carboxylate and alcohol, or metal alkoxy group-containing compound and carboxyl group simultaneously with or after the addition of the reducing substance). The compound is added to at least one of the containing compounds), and after the addition, the mixed system of the starting materials is brought to a high temperature state. That is, it is important that the thiol compound coexists in the mixed system at the time when the mixed system of the starting materials is brought to a high temperature state. Accordingly, the mixed system of the starting materials necessarily includes the thiol compound (in the case where the mixed system is a pre-reacted material as described later, it may be changed to a compound derived from the thiol compound). It will be.
[0058]
In the second production method of the present invention, the metal sulfide is generated by bringing the mixed system of the starting materials to a high temperature state.
In the second production method of the present invention, the mixed system of the starting materials is a mixed system of raw materials that essentially require the combination C or the combination D as described above, and the combination C or the combination D is It means a mixture obtained by mixing essential raw materials and / or a pre-reacted product obtained from raw materials essential for the combination C or the combination D. A part of the mixed system may be a preliminary reaction product, and the other may be a mixture of the starting materials.
[0059]
The preliminary reaction product is a reaction product obtained by reacting the metal carboxylate, the alcohol, the reducing substance, and the thiol compound in the combination C, or the metal alkoxy group-containing compound, the carboxyl group-containing compound, the reducing substance, and the thiol in the combination D. It is a reaction intermediate in the state of any stage until metal sulfide is formed as a reactant by reaction with a compound (state before formation of metal sulfide is recognized) It is a precursor (metal sulfide precursor). That is, the pre-reacted material is a metal sulfide precursor that is neither one of the above-described raw materials nor a metal sulfide to be generated. Such a pre-reacted product can be obtained immediately by simply mixing the raw materials, or the mixture of the raw materials is brought into a moderately high temperature state (a state lower than the temperature at which the metal sulfide is obtained). Is obtained.
[0060]
The mixed system is preferably a fluid liquid such as a paste, suspension, or solution, and a reaction solvent may be used as a starting material if necessary. Specifically, when part or all of the raw materials composed of the combination C or the combination D are mixed, or when the mixed system composed of these raw materials is brought to a high temperature state, a reaction solvent is further added. do it.
When the reaction solvent is also used, the amount used is not particularly limited, but considering the economically obtaining metal sulfide, the amount used of the metal carboxylate or metal alkoxy group-containing compound is It is preferable to be 0.1 to 50% by weight based on the total weight including the solvent.
[0061]
As the reaction solvent, a solvent other than water, that is, a non-aqueous solvent is preferable. Specific examples of the non-aqueous solvent are the same as those exemplified in the first production method of the present invention.
As the reaction solvent in the case of the combination C, an alcohol solvent is particularly preferable among the non-aqueous solvents described above, and an alcohol used as an alcohol as an essential starting material may be used as a solvent.
Specific examples of preferable reaction solvents for the combination D are the same as those exemplified as preferable reaction solvents for the combination B in the first production method of the present invention.
[0062]
When producing a metal sulfide, it is preferable that the amount of water contained in the mixed system is small because defects of the resulting metal sulfide are reduced. Specifically, when the combination C is used as a raw material, it is preferable that the water / metal carboxylate in the mixed system contains only a small amount of water with a metal atom (molar ratio) of less than 4; The ratio is more preferably less than 1, and particularly preferably less than 0.5. On the other hand, when the combination D is used as a raw material, it is preferable that the moisture / metal alkoxy group-containing compound in the mixed system contains only a small amount of moisture with a metal atom (molar ratio) of less than 1, and the molar ratio is More preferably, it is less than 0.2, and it is especially preferable that it is less than 0.1.
[0063]
In the second production method of the present invention, to bring the mixed system into a high temperature state is to raise the temperature of the mixed system to a temperature higher than room temperature (temperature at which the metal sulfide is generated). The temperature in the high temperature state (temperature at which the metal sulfide is generated) varies depending on the type of metal sulfide to be obtained, but is usually 50 ° C. or higher. In order to obtain a metal sulfide with high crystallinity, 100 More preferably, the temperature is in the range of 100 to 300 ° C. In particular, when a metal sulfide is to be obtained as a film as will be described later and an organic material substrate such as a polymer film is used as the substrate, it is preferably in the range of 100 to 200 ° C. More preferably, it is the range of 100-150 degreeC.
[0064]
As specific temperature raising means for bringing the mixed system into a high temperature state (including a temperature raising means for bringing the preliminary reaction product into a moderately high temperature state), heating by a heater, warm air or hot air is possible. Although it is general, it is not limited to this, For example, means, such as ultraviolet irradiation, can also be employ | adopted. When heating to a high temperature state, it may be performed under normal pressure, under pressure, or under reduced pressure, and although not particularly limited, the boiling point of the reaction solvent or the like is lower than the temperature at which the metal sulfide is generated. In this case, it is also preferable to use a pressure resistant reactor. Usually, the reaction temperature and the gas phase pressure during the reaction are carried out below the critical point of the solvent component, but it can also be carried out under supercritical conditions.
[0065]
In the second production method of the present invention, it is preferable that a basic substance is present in the mixed system in the high temperature state. Thereby, a metal sulfide can be generated at a lower temperature.
Examples of the basic substance include amino group-containing compounds; metal ions of alkali metals and alkaline earth metals; hydroxides; oxides; salts of weak acids such as carbonic acid (hydrogen) salts and carboxylates; Preferred examples include alkaline earth metal alkoxides; organometallic complexes such as β-diketone complexes and β-ketoester complexes such as alkali metals and alkaline earth metal metal acetylacetonates; In addition, as an amino group containing compound, the thing similar to what was illustrated as a reducing substance is mentioned. Among these, alkanolamine is particularly preferable. In addition, a basic substance may use only 1 type and may use 2 or more types together.
[0066]
The amount of the basic substance used is not particularly limited, but is preferably 0.01 to 5 times the total number of metal atoms of the metal carboxylate or metal alkoxy group-containing compound. , 0.05 to 2 moles is more preferable.
In the second production method of the present invention, the mixing system (the mixture of the raw materials in the combination C or the combination D and / or the preliminary reaction product of the raw materials in the combination C or the combination D) is obtained, The temperature rise when the mixed system is brought to a high temperature state (including the temperature rise when the pre-reacted material is obtained by mixing each raw material and a gentler high temperature state, and when the preliminary reaction product is brought to a moderately high temperature state) May be performed separately or simultaneously (including part simultaneously), and is not particularly limited. Specifically, for example, 1) after mixing each component (each raw material in combination C or combination D, and reaction solvent as necessary) (reducing substance and thiol compound are mixed according to the order described above), The temperature of the mixture is raised to a predetermined temperature. 2) The alcohol or carboxyl group-containing compound is heated to a predetermined temperature, and the other raw materials are mixed with this while maintaining the temperature (for reducing substances and thiol compounds). (In this case, the reaction solvent may be heated together with the metal carboxylate or metal alkoxy group-containing compound, or may be mixed with other raw materials) and 3) the reaction solvent A metal carboxylate or a metal alkoxy group-containing compound is mixed and heated to a predetermined temperature, and the temperature is maintained while maintaining the temperature. 4) Mix each component (reducing substance and thiol compound in the order described above) 4) Each component (each component C or each material in combination D, and reaction solvent as necessary) is separately raised to a predetermined temperature. Preferably, after warming, these are mixed (reducing substance and thiol compound are mixed in the order described above).
[0067]
<Method for producing third metal sulfide>
The third method for producing a metal sulfide of the present invention uses metal fine particles and a thiol compound as essential starting materials.
Specific examples of the metal fine particles include 1A group, 2A group, 3A group, 4A group, 5A group, 6A group, 7A group, 8 group, lanthanoid element, actinoid element, 1B group, 2B group, 3B. Metal fine particles of metal elements included in Group 4, 4B, 5B, and 6B. Among these, for example, Sr, Ce, Y, Ti, V, Nb, Ta, Cr, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, Cd, Metal fine particles made of metal elements such as Al, Ga, In, Ge, Sn, Sb and La are suitable. Moreover, alloy fine particles can also be used as the metal fine particles. These metal fine particles may use only 1 type and may use 2 or more types together.
[0068]
As the metal fine particles are finer or more porous (that is, the specific surface area is larger), the generation of metal sulfide is completed in a short time, and ultrafine metal sulfide having a uniform particle diameter is obtained. In addition, a metal sulfide film having excellent flatness can be obtained. Accordingly, the metal fine particles preferably have a specific surface area diameter of 100 nm or less, and more preferably 20 nm or less.
Specific examples of the thiol compound include those exemplified as the A2 component of the combination A in the first production method of the present invention. In addition, a thiol compound may use only 1 type and may use 2 or more types together.
[0069]
The ratio of the amount of the metal fine particles and the thiol compound used is not particularly limited, and the molar ratio of the total number of thiol groups in the thiol compound to the total number of metal atoms in the metal fine particles (thiol group / metal atom) will be obtained. The molar ratio of the sulfur atom (S) to the metal atom (M) in the metal sulfide (metal sulfide S / M ratio) may be equal to or greater than the metal sulfide. The S / M ratio is preferably 1 to 100 times, and more preferably 1 to 5 times.
In the third production method of the present invention, the metal sulfide is generated by bringing the mixed system of the starting materials to a high temperature state.
[0070]
In the third production method of the present invention, the starting material mixed system means a mixture obtained by mixing the starting materials and / or a pre-reacted material obtained from the starting materials. A part of the mixed system may be a preliminary reaction product, and the other may be a mixture of the starting materials.
The pre-reacted product is a reaction intermediate in the state of an arbitrary stage until the metal sulfide is generated as a reaction product by the reaction between the metal fine particles and the thiol compound (the state before the formation of the metal sulfide is recognized). And a precursor to the metal sulfide produced (metal sulfide precursor). That is, the preliminary reaction product is a metal sulfide precursor that is neither a metal fine particle nor a thiol compound, and is not a metal sulfide to be produced. Such a pre-reacted material can be obtained immediately by simply mixing the metal fine particles and the thiol compound, or the mixture of the metal fine particles and the thiol compound can be obtained at a moderately high temperature (lower than the temperature at which the metal sulfide is obtained). It is obtained by setting the temperature).
[0071]
The mixed system is preferably a fluid liquid such as a paste, suspension, or solution, and a reaction solvent may be used as a starting material if necessary. Specifically, when mixing the starting material composed of the metal fine particles and the thiol compound, or when bringing the mixed system composed of these starting materials into a high temperature state, it may be carried out after further adding a reaction solvent. .
When the reaction solvent is also used, the amount used is not particularly limited. However, in consideration of obtaining metal sulfides economically, the amount of metal fine particles used is based on the total weight including the reaction solvent. It is preferable to make it 0.1 to 50 weight%.
[0072]
As the reaction solvent, a solvent other than water, that is, a non-aqueous solvent is preferable. Specific examples of the non-aqueous solvent are the same as those exemplified in the first production method of the present invention.
Preferred specific examples of the reaction solvent are the same as those exemplified as preferred reaction solvents in the case of the combination B in the first production method of the present invention.
When producing a metal sulfide, it is preferable that the amount of water contained in the mixed system is small because defects of the resulting metal sulfide are reduced. Specifically, in the case where the combination C is used as a raw material, it is preferable that the water content in the mixed system / the metal atom (molar ratio) in the metal fine particles contain only a small amount of water of less than 4, and the molar ratio is More preferably, it is less than 1, and it is especially preferable that it is less than 0.5. On the other hand, when the combination D is used as a raw material, it is preferable that the water content in the mixed system / the metal atom (molar ratio) in the metal fine particles contains only a small amount of water less than 1, and the molar ratio is 0.2. Is more preferably less than 0.1, and particularly preferably less than 0.1.
[0073]
In the third production method of the present invention, to bring the mixed system into a high temperature state is to raise the temperature of the mixed system to a temperature higher than room temperature (a temperature at which a metal sulfide is generated). The temperature in the high temperature state (temperature at which the metal sulfide is generated) varies depending on the type of metal sulfide to be obtained, but is usually 50 ° C. or higher. In order to obtain a metal sulfide with high crystallinity, 100 More preferably, the temperature is in the range of 100 to 300 ° C. In particular, when a metal sulfide is to be obtained as a film as will be described later and an organic material substrate such as a polymer film is used as the substrate, it is preferably in the range of 100 to 200 ° C. More preferably, it is the range of 100-150 degreeC.
[0074]
As specific temperature raising means for bringing the mixed system into a high temperature state (including a temperature raising means for bringing the preliminary reaction product into a moderately high temperature state), heating by a heater, warm air or hot air is possible. Although it is general, it is not limited to this, For example, means, such as ultraviolet irradiation, can also be employ | adopted. When heating to a high temperature state, it may be performed under normal pressure, under pressure, or under reduced pressure, and although not particularly limited, the boiling point of the reaction solvent or the like is lower than the temperature at which the metal sulfide is generated. In this case, it is also preferable to use a pressure resistant reactor. Usually, the reaction temperature and the gas phase pressure during the reaction are carried out below the critical point of the solvent component, but it can also be carried out under supercritical conditions.
[0075]
In the 3rd manufacturing method of this invention, it is preferable to make a basic substance exist in the said mixed system in the said high temperature state. Thereby, a metal sulfide can be generated at a lower temperature.
Specific examples and preferred examples of the basic substance include those described above as the basic substance in the second production method of the present invention. In addition, a basic substance may use only 1 type and may use 2 or more types together.
The amount of the basic substance used is not particularly limited, but is preferably 0.01 to 5 times mol, and 0.05 to 2 times mol with respect to the total number of moles of metal atoms in the metal fine particles. More preferably.
[0076]
In the third production method of the present invention, the mixing system (the mixture of the metal fine particles and the thiol compound and / or the preliminary reaction product of the metal fine particles and the thiol compound) is mixed, and the mixing system is heated at a high temperature. Separately from the temperature rise when making the state (including the temperature rise when making the pre-reacted material by mixing each raw material and making it a moderately high temperature state, and making it a moderately high temperature state) It may be performed simultaneously (including part simultaneously), and is not particularly limited. Specifically, for example, 1) After mixing the metal fine particles and the thiol compound and, if necessary, the reaction solvent, the mixture is heated to a predetermined temperature, and 2) the thiol compound is heated to a predetermined temperature. While maintaining this temperature, metal fine particles are mixed with this (in this case, the reaction solvent may be heated with the thiol compound or mixed with the metal fine particles), 3) the reaction solvent and the metal Mix fine particles, raise the temperature to a predetermined temperature, and mix the thiol compound with this while maintaining the temperature. 4) Separate the metal fine particles and the thiol compound, and if necessary, the reaction solvent to the predetermined temperature. Preferably, these are mixed after the temperature has been raised.
[0077]
In the first to third production methods of the present invention described above, when the starting material contains two or more kinds of metal components, a metal sulfide containing two or more kinds of metal elements, for example, a composite metal sulfide, a solid solution A metal sulfide or a mixture of two or more metal sulfides can be obtained.
The composite metal sulfide means that the crystal structure (X-ray diffraction pattern or electron diffraction pattern) is substantially different from the single metal sulfide of each metal depending on the metal composition ratio. .
The solid solution metal sulfide has its crystal structure (X-ray diffraction pattern or electron beam diffraction pattern) belonging to the metal sulfide (matrix) of the main metal component, and a metal component other than the main metal component (dopant metal) ) Contained in the base metal sulfide, either in the form of substitution with a part of the main component metal (substitutional solid solution) or in the form of a gap in the crystal lattice (interstitial solid solution) It is what is done. The base metal sulfide may be a single metal sulfide or a composite metal sulfide. The content of the dopant metal in the solid solution metal sulfide is usually in the range of 0.01 to 30 atomic% with respect to the main component metal.
[0078]
The solid solution metal sulfide is effective for controlling various characteristics such as light absorption characteristics, light emission characteristics, electrical conduction characteristics, and magnetic characteristics. For example, a metal sulfide in which 0.1 to 1% of a luminescent metal ion such as Mn, Sb or rare earth metal is preferably dissolved as a dopant metal is useful as a luminescent material exhibiting light emission (fluorescence) characteristics. As a metal, a metal sulfide in which magnetic metal ions such as Co, Fe, Ni, and Mn are preferably dissolved in an amount of preferably 1 to 30% can be expected to have diluted magnetic semiconductor characteristics. When light emission (fluorescence) characteristics or dilute magnetic semiconductor characteristics are desired, the base metal sulfide is preferably a composition having a high visible light transmission property. For example, a metal sulfide such as Zn or Y is used. Is preferred.
[0079]
When the composite metal sulfide is to be obtained, in the first and second production methods, two or more kinds having different metal elements among the starting materials may be appropriately selected. In the third production method, at least one metal fine particle and any metal element-containing compound (any of the starting materials containing the metal element in the first and second production methods) may be used. However, alloy fine particles may be used as the metal fine particles. However, when alloy fine particles are used, a composite metal sulfide can be obtained with only metal fine particles, and unreacted substances of other metal element-containing compounds remain. This is preferable because there is no fear. As the metal element-containing compound, the metal dithiocarboxylate and the thio-s-carboxylate are preferable.
[0080]
When trying to obtain the solid solution metal sulfide, as a raw material to be a dopant metal, in the first and second production methods, any one of the starting raw materials containing the metal element in the first and second production methods ( However, in the case of a metal (thio) alkoxy group-containing compound, m = 0 is preferably used. However, it is preferable to use a metal element that is essential in the production method (combination of starting materials) to be employed. It is better to use raw materials. In the third production method, any metal element-containing compound (any of the starting materials containing the metal element in the first and second production methods. However, in the case of a metal (thio) alkoxy group-containing compound, m = 0 may be used as the dopant metal, or alloy fine particles may be used as the metal fine particles. However, when alloy fine particles are used, a composite metal sulfide can be obtained with only metal fine particles. This is preferable because unreacted substances of other metal element-containing compounds do not remain. When using a metal element-containing compound, the metal (thio) alkoxy group-containing compound (m = 0), the metal dithiocarboxylate, and the thio-s-carboxylate are particularly preferable.
[0081]
In the above first to third production methods of the present invention, the metal sulfide to be generated may be obtained in the form of particles, or the metal sulfide to be generated is fixed on the surface of the substrate as a film. You may do it.
When the produced metal sulfide is obtained in the form of particles, it is preferably 1 to 100 nm, and more preferably 1 to 20 nm. When the average particle size is less than 1 nm, various properties expected from metal sulfides (particularly, light emission properties) are difficult to obtain. On the other hand, when the average particle size exceeds 100 nm, the dispersion stability of the dispersion of the particles is insufficient. Thus, film formability and the like are likely to deteriorate.
[0082]
In each of the above production methods, the metal sulfide is generated as particles in a reaction liquid (dispersion) obtained by bringing the mixed system to a high temperature state. Specifically, according to each production method of the present invention, the reaction liquid (dispersion liquid) in which the metal sulfide particles controlled to the average particle diameter are dispersed in an amount of 0.1 to 50% by weight, preferably 1 to 20% by weight. ) Is obtained. Therefore, when the metal sulfide is to be obtained as particles (powder), the obtained reaction solution (dispersion) may be used for ordinary separation means such as centrifugation or filtration. Further, the obtained reaction liquid (dispersion liquid) is used as a concentrated liquid of a desired concentration by using an ultrafiltration membrane or by removing a part of the solvent by heating, or processed into a paste form and used. You can also Further, the reaction liquid (dispersion), the concentrated liquid, or the paste-like processed product is heated in the presence of a desired solvent to obtain the reaction liquid (dispersion), the concentrated liquid, or the paste-like processed material. The solvent initially contained in the product may be removed and replaced with a desired solvent. Such a reaction liquid (dispersion), concentrated liquid, or paste-like processed product should be suitably used as a film forming material or coating material for a metal sulfide film as it is or by mixing a binder component or the like as necessary. Can do.
[0083]
In the case where the metal sulfide to be produced is fixed on the surface of the substrate as a film, the mixed system is brought into contact with the substrate, and the contact system is brought to a high temperature state to produce the metal sulfide. (Hereinafter, referred to as “Method I”), a method in which the mixed system is applied to the surface of the substrate while maintaining the high temperature state or in a high temperature state (hereinafter referred to as “Method II”). ), And the like. In the case of the method I, more specifically, the method of bringing the contact system to a high temperature state is a method of applying the mixed system to the surface of the substrate and bringing the substrate to a high temperature state (hereinafter, “method”). I-1 "), and the method of immersing the substrate in the mixed system to bring it to a high temperature state (hereinafter referred to as" Method I-2 "). Method I-1 and Method II are methods in which the mixed system is applied to the surface of the substrate. In Method I-1, after application, in Method II, the mixed system is brought to a high temperature state before or during application. In this way, the metal sulfide is fixed on the surface of the substrate to form a metal sulfide layer. On the other hand, in the method I-2, a metal sulfide is deposited and grown on the surface of the base material by bringing the mixed system to a high temperature state in a state where the base material is immersed in the mixed system. In this method, a sulfide is fixed and a metal sulfide layer is formed. Hereinafter, method I-1 and method II will be described as a coating method, and method I-2 will be described as an immersion method.
[0084]
In the coating method, in the method I-1, after applying to the base material of the mixed system, in the method II, the mixed system is brought to a high temperature state before or during the coating to the base material of the mixed system. There are no particular restrictions on the timing of mixing when obtaining the composition, raising the temperature when forming a high temperature, and applying to the substrate. However, when the mixed system includes a pre-reacted material, the pre-reacted material tends not to exist in a dissolved state at room temperature for a long time. It is preferable to apply. In addition, a mode in which Method II and Method I-1 are combined is also preferable, and it is preferable that the temperature of the base material is further increased after applying a mixed system whose temperature has been increased before or during application to the base material.
[0085]
As a specific example of the mode in which the mixed system is brought into a high temperature state during application to the substrate of the mixed system in the method II, for example, the mixed system is passed through a heated pipe directly connected to the coated portion of the substrate. However, the present invention is not particularly limited to these. Examples include a form in which the mixture is heated and applied, and a form in which the mixed system is heated in a pan of a roll coater and applied to the substrate while being heated. As a specific example of a mode in which the mixed system is brought into a high temperature state before application to the mixed system substrate in Method II, for example, the mixed system is heated using a (pressure-resistant) batch reactor or the like. The form applied to the base material is not particularly limited.
[0086]
When the coating method is employed and the reaction system contains a reaction solvent, the boiling point at normal pressure is higher than the temperature at which the metal sulfide is generated (temperature when the metal sulfide is brought into a high temperature state) as the reaction solvent. It is preferable to select a reaction solvent. Thereby, a metal sulfide layer excellent in transparency and a metal sulfide layer having a high sulfide content can be easily obtained. Further, in this case, the content of the reaction solvent is preferably equimolar or more, more preferably twice or more molar in terms of molar ratio to the metal in the mixed system. When the coating method is employed and the reaction system contains a reaction solvent, it is preferable to select a non-aqueous solvent that can be azeotroped with water as the reaction solvent. Thereby, a dense metal sulfide layer can be easily formed at a lower temperature. In this case, the content of the reaction solvent is preferably equimolar or more, more preferably 2 times or more, and further preferably 5 times or more, in terms of the molar ratio to the metal in the mixed system. In the coating method, the metal oxide layer is formed by heating, and the reaction solvent and the like can be volatilized and removed.
[0087]
In the coating method, the method for coating the mixed system on the substrate is not particularly limited, and specifically, for example, a bar coater method, a roll coater method, a knife coater method, a die coater method, a spin coat method. A conventionally known method such as a dipping method may be employed.
In the coating method, when a high temperature state is set, only the substrate may be heated, only the coated surface may be heated, or both the substrate and the coated surface are heated. There is no particular limitation.
In the coating method, when adopting a form in which the method II and the method I-1 are combined, the temperature when the high temperature state is set before coating or during coating is preferably a temperature at which a preliminary reaction product is generated. Is preferably not less than 50 ° C. and not more than the temperature at which a high temperature state is obtained after coating.
[0088]
In the coating method, the heating time for making the high temperature state is not particularly limited, and specifically, 10 seconds to 1 hour is preferable, but the crystallinity is increased or the adhesion to the substrate is improved. For the purpose of increasing the temperature, it may be further aged by heating. There are no particular limitations on the temperature, time, and temperature raising means during aging, and these may be selected as appropriate.
The coating method is suitable for obtaining a continuous layer, in particular, a dense continuous metal sulfide layer with high surface smoothness.
In the immersion method, the substrate may be immersed in the mixed system until the metal sulfide is completely formed, preferably before the metal sulfide formation reaction is started. There are no particular restrictions on the mixing timing, the temperature rise in the high temperature state, and the timing of immersion of the substrate. However, when the mixed system includes a pre-reacted material, the pre-reacted material tends not to exist in a dissolved state at room temperature for a long time. It is preferable to immerse.
[0089]
In the immersion method, a commonly used apparatus can be used, but a device having a function of fixing the substrate is preferable. For example, a batch reaction apparatus in which a substrate (base material) holder is installed can be used. The presence or absence of stirring and the stirring conditions are not particularly limited, and may be appropriately selected.
In the immersion method, when the high temperature state is set, the temperature of the entire mixed system may be increased while the base material is immersed, or only the base material may be selectively selected while the base material is immersed. Although the temperature may be raised, selective heating of only the base material is more likely to cause a reaction on the surface of the base material, and a metal sulfide layer with high adhesion is formed on the surface of the base material. It is preferable because it is easily done.
[0090]
The immersion method is suitable for obtaining a discontinuous layer or a continuous metal sulfide layer having a porous structure. However, depending on the temperature at the time of high temperature and the type of raw material, the macro structure of the metal sulfide layer (continuous layer or discontinuous layer, whether it is excellent in denseness or porous), The crystal structure (crystallite size, shape, etc.) can be controlled.
The material for obtaining the metal sulfide to be fixed on the surface of the substrate as a film is not particularly limited, and specifically, for example, oxide, nitride, carbide Ceramics such as glass, inorganic materials such as glass; polyester resins such as PET, PBT, PEN, polycarbonate resins, polyphenylene sulfide resins, polyethersulfone resins, polyetherimide resins, polyimide resins, amorphous polyolefin resins, polyarylate resins, aramid resins , Polyetheretherketone resin, (meth) acrylic resin, PVC resin, PVDC resin, PVA resin, EVOH resin, polyimide resin, polyamideimide resin, PTFE, PVF, PGF, ETFE and other fluororesin, epoxy resin, polyolefin resin, etc. Various resins , Aluminum in these various resins, alumina, organics processed products with such a deposited silica; various metals; and the like preferably. Specific examples of the form include, but are not limited to, a film form, a sheet form, a plate form, a fiber form, and a laminate form. The substrate is not particularly limited in terms of function, and specifically, is optically transparent and opaque; electrically is an insulator, a conductor, a p-type or n-type semiconductor, or a dielectric. The magnetic field is selected according to the purpose.
[0091]
In the first to third production methods of the present invention, when the resulting metal sulfide is fixed on the surface of the substrate as a film and the obtained metal sulfide has an organic group, Furthermore, you may make it remove the organic group which this metal sulfide layer has by performing the following processes. That is, a process for decomposing an organic group by heating in a gas phase (in an oxidizing atmosphere such as air, a reducing atmosphere, or an inert atmosphere), or a process for decomposing an organic group by heating in a liquid phase , Decomposition by a chemical method using an acidic or basic aqueous solution, heat treatment in the presence of an alcohol when the organic group is a carboxyl group, heat treatment in the presence of acetic acid when the organic group is an alkoxy group, These include high-energy ultraviolet irradiation treatment with ultraviolet rays having a wavelength of 300 nm or less (particularly, wavelength of 200 nm or less) effective for organic chain scission, treatment with corona discharge, and the like. In addition, when performing the said high energy ultraviolet irradiation process, it is preferable to use the low pressure mercury lamp which contains many ultraviolet rays of a short wavelength (high energy) rather than a high pressure mercury lamp.
[0092]
When the produced metal sulfide is fixed as a film on the surface of the substrate, the thickness of the metal sulfide layer (thickness in the direction perpendicular to the surface of the substrate) is not particularly limited, but is usually 1 nm. It is preferable that it is -1000 micrometers, More preferably, it is 1 nm-10 micrometers.
The metal sulfide (particle or film) obtained by the first to third production methods of the present invention has an excellent conductive function, photoconductive function, light emitting function, magnetic function, magnetooptical function, etc. It can be suitably used as LED films, phosphor films, conductive films, (dilute) magnetic semiconductor films, ferromagnetic films, etc. for recording and storage elements.
[0093]
【Example】
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. In the following, “parts by weight” may be simply referred to as “parts” for convenience.
<Manufacture of metal sulfide particles>
The analysis of the particle dispersion obtained in the following examples was performed as follows.
(Preparation of powder sample) After the particles in the dispersion were separated by a centrifugal separation operation, washed with acetone, and then vacuum-dried at 60 ° C for 24 hours to completely remove volatile components to obtain a fine powder. This was used as a powder sample.
[0094]
(Crystal structure and identification of particles) By performing powder X-ray diffraction measurement of a powder sample, or field emission transmission electron microscope observation and electron diffraction measurement using a dispersion liquid developed on a sample stage as a sample, The crystal structure of was determined. Furthermore, while observing the dispersion liquid developed on the sample stage with a field emission transmission electron microscope as a sample, elemental analysis is performed using XMA that can narrow down the spot with a maximum resolution of 1 nmφ, thereby identifying the metal species. The composition was determined by quantifying the ratio of sulfur atom / metal atom.
(Average particle diameter) It measured with the field emission type | mold transmission electron microscope using the dispersion liquid as a sample. However, when it was difficult to measure with a field emission transmission electron microscope, the crystallite diameter (Dw) or specific surface area diameter (Ds) measured as follows was used as the average particle diameter. That is, the crystallite diameter (Dw) was determined by the Wilson method by performing powder X-ray diffraction measurement of a powder sample. Regarding the particles that were amorphous in the powder X-ray diffraction measurement of the powder sample, E. T.A. The specific surface area and true specific gravity were measured by the method, and the specific surface area diameter (Ds) was determined from the following formula.
[0095]
Ds = 6000 / (ρ · S)
Ds: specific surface area diameter [nm], ρ: true specific gravity, S: specific surface area [m²/ G]
(Particle concentration in the dispersion) The particles in the dispersion were separated by centrifugation, then washed with acetone, and then vacuum dried at 60 ° C for 24 hours. The particle concentration inside was calculated.
(Metal content ratio) If the particles are considered to contain two or more metal components, perform X-ray fluorescence analysis of the powder sample, quantify the content of each metal, and calculate the content ratio of each metal. did.
[0096]
(Reference Example-Synthesis of zinc bis (thio-s-acetic acid))
Using a reactor similar to Example 1A-1 described later, 10 parts of zinc acetate anhydride and 200 parts of thio-s-acetic acid were charged into the reactor, and the gas phase part in the reactor was purged with nitrogen gas. Then, the temperature was raised with stirring, and the mixture was heated under pressure at 150 ° C. for 10 hours. At this time, acetic acid liberated / generated during heating was appropriately distilled off from the reaction system. After completion of the heating, the obtained reaction solution was concentrated by heating with an evaporator, and the resulting precipitate was filtered, washed with thio-s-acetic acid, and then vacuum-dried to obtain zinc bis (thio-s-acetic acid). Got.
[0097]
In addition, other metal thio-s-carboxylates and metal dithiocarboxylates in the following examples were synthesized in the same manner as in the reference examples.
(Example 1A-1)
A pressure-resistant glass reactor (capacity 1 liter) equipped with a stirrer, an addition port, a thermometer, a distillate gas outlet, and a nitrogen gas inlet, and an addition directly connected to the addition port via a ball valve A trap filled with an aqueous sodium hydroxide solution directly connected to the tank and distillate gas outlet via a pressure valve (set to 2 MPa) (when the pressure in the reactor exceeds 2 MPa due to the gas generated by the reaction, A pressure-resistant batch type reaction apparatus equipped with a solvent that is distilled off and collected in the trap was prepared.
[0098]
In the reactor, 30 parts of zinc bis (thio-s-acetic acid) as raw material I (A1 component) and 328 parts of n-hexanethiol as raw material II (A2 component) were charged, and the gas phase part in the reactor After purging with nitrogen gas, the temperature was raised from 20 ° C. to 150 ° C. over 60 minutes with stirring in a sealed state. After maintaining at 150 ° C. ± 2 ° C. for 1 hour under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 350 parts of a particle dispersion.
When the particles in the obtained dispersion were analyzed, the particles were ZnS particles composed of a single crystal having an average particle diameter of 10 nm, and the particle concentration in the dispersion was 3.8% by weight.
[0099]
(Examples 1A-2 to 1A-12)
Using the same reaction apparatus as in Example 1A-1, the types and amounts of raw material I and raw material II, the temperature at the time of temperature increase were changed as shown in Table 1, and the solvents shown in Table 1 together with raw materials I and II were changed. A dispersion was obtained in the same manner as in Example 1A-1, except that the reactor was charged and the heating temperature at which the temperature was raised was changed as shown in Table 1. Table 2 shows the amount of the obtained dispersion and the analysis result of the dispersion. Example 1A-1 is also shown in Tables 1 and 2.
In Table 1, the following abbreviations were used.
PGMAC: Propylene glycol methyl ether acetate
EGEAC: Ethylene glycol ethyl ether acetate
MBA: 3-methoxybutyl acetate
DBE: Dibenzyl ether
MIBK: Methyl isobutyl ketone
BA: Butyl acetate
TOL: Toluene
PGDM: Propylene glycol dimethyl ether
[0100]
[Table 1]

[0101]
[Table 2]

[0102]
(Example 1A-13)
Using the same reactor as in Example 1A-1, in the reactor, 15 parts of copper (II) ethoxide as raw material I (B1 component), 74 parts of thio-s-acetic acid as raw material II (B2 component), After adding 250 parts of propylene glycol methyl ether acetate as a solvent and purging the gas phase part in the reactor with nitrogen gas, the temperature was raised from 20 ° C. to 180 ° C. over 60 minutes with stirring in a sealed state. After maintaining at 180 ° C. ± 2 ° C. for 1 hour under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 329 parts of a particle dispersion.
[0103]
When the particles in the obtained dispersion were analyzed, the particles were CuS particles composed of a single crystal having an average particle diameter of 8 nm, and the particle concentration in the dispersion was 2.8% by weight.
(Example 1A-14)
Using the same reactor as in Example 1A-1, 20 parts of copper (I) thiophenoxide (manufactured by Wako Pure Chemical Industries, Ltd.) as raw material I (B1 component) and hexanedithio as raw material II (B2 component) are used in the reactor. After charging 34 parts of acid and 300 parts of 3-methoxybutyl acetate as a solvent, and purging the gas phase part in the reactor with nitrogen gas, the mixture was stirred at 20 ° C. over 60 minutes while stirring at 150 ° C. over 150 minutes. The temperature was raised to. After maintaining at 150 ° C. ± 2 ° C. for 1 hour under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 360 parts of a particle dispersion.
[0104]
When the particles in the obtained dispersion were analyzed, the particles were Cu made of a single crystal having an average particle diameter of 3 nm.₂S particles, and the particle concentration in the dispersion was 2.6% by weight.
(Example 1A-15)
Using the same reaction apparatus as in Example 1A-1, 20 parts of copper (II) dimethylamino ethoxide as raw material I (B1 component) and p- [methoxy (thio (thiol) as raw material II (B2 component) are contained in the reactor. Carbonyl)] dithiobenzoic acid 46 parts and 250 parts of ethylene glycol ethyl ether acetate as a solvent were charged, and the gas phase part in the reactor was purged with nitrogen gas. The temperature was raised to 150 ° C. over a period of minutes. After maintaining at 150 ° C. ± 2 ° C. for 1 hour under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 350 parts of a particle dispersion.
[0105]
When the particles in the obtained dispersion were analyzed, the particles were CuS particles composed of a single crystal having an average particle diameter of 15 nm, and the particle concentration in the dispersion was 2.5% by weight.
(Example 1B-1)
Using the same reaction apparatus as in Example 1A-1, in the reactor, 22 parts of palladium acetate (II) as raw material I (metal carboxylate), 500 parts of methanol as raw material II (alcohol), and raw material III ( 14 parts of monoethanolamine as the reducing substance) and 24 parts of 1,4-butanedithiol as the raw material IV (thiol compound) were charged, and the gas phase in the reactor was purged with nitrogen gas, and then stirred in a sealed state. However, the temperature was raised from 20 ° C. to 150 ° C. over 60 minutes. After holding at 150 ° C. ± 2 ° C. for 10 minutes under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 565 parts of a particle dispersion.
[0106]
When the particles in the obtained dispersion were analyzed, the particles were PdS particles composed of a single crystal having an average particle diameter of 8 nm, and the particle concentration in the dispersion was 2.4% by weight.
(Example 1B-2)
Using the same reaction apparatus as in Example 1A-1, 28 parts of 2-dibutylamino-4,6-dimercapto-S-triazine (dibutyltriazinedithiol) and 2-butoxyethanol as raw material I (thiol compound) are added to the addition tank. A mixed solution consisting of 100 parts was charged, the gas phase part in the addition tank was purged with nitrogen gas, and then pressurized to 0.2 MPa with nitrogen gas. Meanwhile, in the reactor, 18 parts of copper (II) acetate as raw material II (metal carboxylate), 400 parts of 2-butoxyethanol as raw material III (alcohol), and monoethanolamine as raw material IV (reducing substance) After 15 parts were charged and the gas phase part in the reactor was purged with nitrogen gas, the temperature was raised from 20 ° C. to 150 ° C. over 60 minutes with stirring in a sealed state. During the temperature increase, when the liquid in the reactor changed to wine red, the mixed solution in the addition tank was added into the reactor over 1 minute. Then, after maintaining at 150 ° C. ± 2 ° C. for 10 minutes under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 560 parts of a particle dispersion.
[0107]
When the particles in the obtained dispersion were analyzed, the particles were Cu single crystal having an average particle diameter of 5 nm.₂S particles, and the particle concentration in the dispersion was 1.4% by weight.
(Example 1B-3)
Using the same reaction apparatus as in Example 1A-1, 100 parts of methoxyethoxyethanol containing 25% by weight of copper (II) methoxyethoxyethoxide as raw material I (metal alkoxy group-containing compound) and raw material II ( The reaction mixture was charged with 12 parts of acetic acid as a carboxyl group-containing compound), 30 parts of n-butylamine as raw material III (reducing substance), 27 parts of thiophenol as raw material IV (thiol compound), and 450 parts of methanol as a solvent. After purging the gas phase portion with nitrogen gas, the temperature was raised from 20 ° C. to 170 ° C. over 60 minutes while stirring in a sealed state. After maintaining at 170 ° C. ± 2 ° C. for 10 minutes under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 615 parts of a particle dispersion.
[0108]
When the particles in the obtained dispersion were analyzed, the particles were Cu single crystal having an average particle diameter of 5 nm.₂S particles, and the particle concentration in the dispersion was 1.0% by weight.
(Example 1C-1)
Using the same reactor as in Example 1A-1, 6 parts of nickel (Ni) fine particles as raw material I (metal fine particles), 400 parts of ethylene glycol monoethyl ether as a solvent, and raw material II (thiol compound) are used in the reactor. ) 30 parts of 2-dibutylamino-4,6-dimercapto-S-triazine and 19 parts of cyclohexylamine as a basic compound, and after purging the gas phase in the reactor with nitrogen gas, While stirring, the temperature was raised from 20 ° C. to 200 ° C. over 60 minutes. After maintaining at 200 ° C. ± 2 ° C. for 5 hours under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 434 parts of a particle dispersion.
[0109]
When the particles in the obtained dispersion were analyzed, the particles were NiS particles composed of a single crystal having an average particle diameter of 15 nm, and the particle concentration in the dispersion was 2.0% by weight.
(Example 1C-2)
Using the same reaction apparatus as in Example 1A-1, in a reactor, 6 parts of copper (Cu) fine particles as raw material I (metal fine particles), 200 parts of propylene glycol mono-t-butyl ether as a solvent, and raw material II ( As a thiol compound), 36 parts of phenylmethanethiol and 1 part of diethanolamine as a basic compound were charged, and after purging the gas phase part in the reactor with nitrogen gas, stirring was performed in a sealed state at 20 ° C. for 60 minutes. The temperature was raised to 200 ° C. After maintaining at 200 ° C. ± 2 ° C. for 5 hours under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 240 parts of a particle dispersion.
[0110]
When the particles in the obtained dispersion were analyzed, the particles were Cu made of a single crystal having an average particle diameter of 6 nm.₂S particles, and the particle concentration in the dispersion was 3.0% by weight.
(Example 1C-3)
Using the same reaction apparatus as in Example 1A-1, in the reactor, 10 parts of silver (Ag) fine particles as raw material I (metal fine particles), 300 parts of dipropylene glycol monoethyl ether as a solvent, and raw material II (thiol) Compound 48) was charged with 48 parts of cyclopentanethiol, and after the gas phase in the reactor was purged with nitrogen gas, the temperature was raised from 20 ° C. to 160 ° C. over 60 minutes with stirring in a sealed state. After maintaining at 160 ° C. ± 2 ° C. for 5 hours under pressure, the mixture was cooled to room temperature (20 ° C.) to obtain 355 parts of a particle dispersion.
[0111]
When the particles in the obtained dispersion were analyzed, the particles were Ag composed of a single crystal having an average particle diameter of 12 nm.₂S particles, and the particle concentration in the dispersion was 3.0% by weight.
<Manufacture of metal sulfide films>
The analysis of the films obtained in the following examples was performed as follows.
(Crystal structure and identification of film) The crystal structure was determined from the value of lattice constant and diffraction pattern by electron diffraction measurement or thin film X-ray diffraction measurement. Furthermore, the metal seed | species was identified by performing the elemental analysis of the film | membrane surface layer and the inner layer after performing an etching process by ESCA measurement. In addition, when it was not able to fully measure with it adhering to a glass plate, the film | membrane was peeled from the glass plate and it measured.
[0112]
(Film thickness) The glass plate to which the film adhered was cut vertically with a glass cutter, the cut surface was observed with an SEM, and the film thickness was measured with an SEM image.
(Example 2A-1)
Using the same reactor as in Example 1A-1, in the reactor, 30 parts of zinc bis (thio-s-acetic acid) as raw material I (A1 component) and n-hexanethiol 66 as raw material II (A2 component) And 300 parts of propylene glycol-t-butyl ether acetate as a solvent, and after purging the gas phase part in the reactor with nitrogen gas, stirring from 20 ° C. to 100 ° C. over 15 minutes. The temperature was raised to. After holding at 100 ° C. ± 2 ° C. for 10 minutes under pressure (0.2 MPa), it was cooled to room temperature (20 ° C.) to obtain a coating solution.
[0113]
Next, after apply | coating the obtained coating liquid to a glass plate with a bar coater, it heated at 150 degreeC for 20 minute (s) by nitrogen atmosphere, and obtained the film | membrane adhering on the glass plate.
When the obtained film was analyzed, the film was a film made of ZnS crystals and the film thickness was 0.1 μm.
(Examples 2A-2 to 2A-9)
Using the same reaction apparatus as Example 1A-1, the raw material I, the raw material II, the kind and quantity of a solvent, the temperature at the time of heating at the time of obtaining a coating liquid (heating temperature), the heating temperature after application | coating on a glass plate ( Except for changing the film forming temperature as shown in Table 3, a film adhered on the glass plate was obtained in the same manner as in Example 2A-1. Table 3 shows the analysis results of the obtained film. Example 2A-1 is also shown in Table 3.
[0114]
In Table 3, the following abbreviations were used.
PGBAC: Propylene glycol-t-butyl ether acetate
EGEAC: Ethylene glycol ethyl ether acetate
MBA: 3-methoxybutyl acetate
EGBAC: ethylene glycol-n-butyl ether acetate
DPGEA: Dipropylene glycol ethyl ether acetate
[0115]
[Table 3]

[0116]
(Example 2A-10)
Using the same reactor as in Example 1A-1, in the reactor, 15 parts of copper (II) ethoxide as raw material I (B1 component), 74 parts of thio-s-acetic acid as raw material II (B2 component), After charging 300 parts of ethylene glycol ethyl ether acetate as a solvent and purging the gas phase part in the reactor with nitrogen gas, the temperature was raised from 20 ° C. to 100 ° C. over 15 minutes while stirring in a sealed state. After holding at 100 ° C. ± 2 ° C. for 10 minutes under pressure (0.1 MPa), it was cooled to room temperature (20 ° C.) to obtain a coating solution.
[0117]
Next, after apply | coating the obtained coating liquid to a glass plate with a bar coater, it heated at 150 degreeC for 20 minute (s) by nitrogen atmosphere, and obtained the film | membrane adhering on the glass plate.
When the obtained film was analyzed, the film was a film made of CuS crystals and the film thickness was 0.2 μm.
(Example 2A-11)
In Example 2A-10, 20 parts of copper (I) thiophenoxide (manufactured by Wako Pure Chemical Industries, Ltd.) as raw material I (component B1), 34 parts of hexanedithioic acid as raw material II (component B2), and 3-methoxybutyl acetate as solvent Except having changed 300 parts so that it may be used, it carried out similarly to Example 2A-10, and obtained the film | membrane adhering on the glass plate.
[0118]
When the obtained film was analyzed, it was found that the film was Cu.₂The film was made of S crystal, and the film thickness was 0.1 μm.
(Example 2A-12)
In Example 2A-10, 20 parts of copper (II) dimethylaminoethoxide as raw material I (component B1) and 114 parts of p- [methoxy (thiocarbonyl)] dithiobenzoic acid as raw material II (component B2) were used as solvents. A film adhered on the glass plate was obtained in the same manner as in Example 2A-10, except that 100 parts of ethylene glycol monoethyl ether acetate and 100 parts of dipropylene glycol ethyl ether acetate were used.
[0119]
When the obtained film was analyzed, it was a film made of CuS crystals and the film thickness was 0.05 μm.
(Example 2A-13)
Except that 30 parts of zinc bis (thio-s-acetic acid) and 0.88 parts of cobalt (II) bis (thio-s-acetic acid) were used as the raw material I (component A1) in Example 2A-1. Obtained the film | membrane adhering on the glass plate similarly to Example 2 A-1.
When the obtained film was analyzed, the film was a film made of ZnS crystals and the film thickness was 0.1 μm. The film contained 3 atomic% Co (II) with respect to Zn.
[0120]
(Example 2A-14)
Except that 30 parts of zinc bis (thio-s-acetic acid) and 0.86 parts of manganese (II) bis (thio-s-acetic acid) were used as raw material I (component A1) in Example 2A-1. Obtained the film | membrane adhering on the glass plate similarly to Example 2 A-1.
When the obtained film was analyzed, the film was a film made of ZnS crystals and the film thickness was 0.1 μm. Moreover, this film | membrane contained 3 atomic% Mn (II) with respect to Zn.
[0121]
(Example 2A-15)
Except that the raw material I in Example 2A-1 was changed to use 12 parts of zinc bis (thio-s-acetic acid) and 14.6 parts of cadmium (II) bis (thio-s-acetic acid). Obtained the film | membrane adhering on the glass plate similarly to Example 2 A-1.
When the obtained film was analyzed, it was found that the film was Zn._0.5Cd_0.5The film was made of S crystal, and the film thickness was 0.1 μm.
(Example 2B-1)
Using the same reactor as in Example 1A-1, 11 parts of palladium acetate (II) as raw material I (metal carboxylate), 500 parts of benzyl alcohol as raw material II (alcohol), and raw material III are used in the reactor. 8 parts of monoethanolamine as (reducing substance) and 12 parts of 2-amino-4,6-dimercapto-S-triazine as raw material IV (thiol compound) are charged, and the gas phase part in the reactor is filled with nitrogen gas. After purging, the temperature was raised from 20 ° C. to 100 ° C. over 60 minutes while stirring in a sealed state. After holding at 100 ° C. ± 2 ° C. for 10 minutes under pressure (0.1 MPa), it was cooled to room temperature (20 ° C.) to obtain a coating solution.
[0122]
Next, after apply | coating the obtained coating liquid to a glass plate with a bar coater, it heated at 150 degreeC for 20 minute (s) by nitrogen atmosphere, and obtained the film | membrane adhering on the glass plate.
When the obtained film was analyzed, it was a film made of PdS crystals and the film thickness was 0.2 μm.
(Example 2B-2)
Using the same reaction apparatus as in Example 1A-1, in the reactor, 18 parts of copper acetate (II) as raw material I (metal carboxylate), 150 parts of methanol as raw material II (alcohol) and ethylene glycol mono- After charging 50 parts of n-butyl ether and 20 parts of monoethanolamine as a raw material III (reducing substance) and purging the gas phase part in the reactor with nitrogen gas, the mixture was stirred at 20 ° C. with stirring in a sealed state. The temperature was raised to 100 ° C. over 15 minutes. Then, it cooled to room temperature (20 degreeC) and obtained the amber solution. To this solution, 150 parts of a THF solution containing 20% by weight of 2-dibutylamino-4,6-dimercapto-S-triazine as a raw material IV (thiol compound) was added and mixed to obtain a coating solution.
[0123]
Next, after dipping and applying a glass plate to the obtained coating solution, the film was heated at 150 ° C. for 20 minutes in a nitrogen atmosphere to obtain a film adhered on the glass plate.
When the obtained film was analyzed, it was found that the film was Cu.₂The film was made of S crystal and the film thickness was 0.2 μm.
(Example 2C-1)
Using the same reaction apparatus as in Example 1A-1, in the reactor, 6 parts of copper (Cu) fine particles as raw material I (metal fine particles), 200 parts of ethylene glycol monoethyl ether as a solvent, and raw material II (thiol compound) ) And 2-dibutylamino-4,6-dimercapto-S-triazine (27 parts) were charged, and the gas phase part in the reactor was purged with nitrogen gas. The temperature was raised to 120 ° C. and held for 2 hours, then cooled to room temperature (20 ° C.), and unreacted copper fine particles were removed by filtration, and 3 parts of monoethanolamine was added as a basic substance to the resulting solution. Was added to obtain a coating solution.
[0124]
Next, after apply | coating the obtained coating liquid to a glass plate with a bar coater, it heated at 150 degreeC for 20 minute (s) by nitrogen atmosphere, and obtained the film | membrane adhering on the glass plate.
When the obtained film was analyzed, it was found that the film was Cu.₂The film was made of S crystal and the film thickness was 0.2 μm.
[0125]
【The invention's effect】
According to the invention, the particlesDiameterA controlled metal sulfide fine particle or a dense metal sulfide thin film can be obtained with excellent productivity, and a metal sulfide production method applicable to various metals can be provided.

Claims (6)

Metal thio-s-carboxylate and / or metal dithiocarboxylate and thiol compound as starting materials, or metal (thio) alkoxy group-containing compound and thio-s-carboxyl group-containing compound and / or A method for producing a metal sulfide, comprising producing a metal sulfide using a dithiocarboxyl group-containing compound as a starting material. In the presence of a reducing substance, a metal carboxylate and an alcohol are used as starting materials, or a metal alkoxy group-containing compound and a carboxyl group-containing compound are used as starting materials, and a metal sulfide is formed in the presence of a thiol compound. A method for producing a metal sulfide, characterized in that it is generated. A method for producing a metal sulfide, comprising producing metal sulfide in the presence of a thiol compound using metal fine particles as a starting material. The method for producing a metal sulfide according to claim 2 or 3, wherein a basic substance is further present when the metal sulfide is produced. The method for producing a metal sulfide according to any one of claims 1 to 4, wherein a metal sulfide having a particle shape and an average particle diameter of 1 to 100 nm is obtained. The method for producing a metal sulfide according to any one of claims 1 to 4, wherein the produced metal sulfide is fixed as a film on the surface of the substrate.