JPWO2008013250A1 - Periodic table group 11 or group 12 metal chalcogenide nanoparticles and method for producing the same - Google Patents
Periodic table group 11 or group 12 metal chalcogenide nanoparticles and method for producing the same Download PDFInfo
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Abstract
本発明は、容易に大量製造が可能な方法にて、液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子を提供する、ならびに工業的に好適な周期表第11族又は第12族金属カルコゲナイドナノ粒子を提供する。The present invention provides periodic table Group 11 or Group 12 metal chalcogenide nanoparticles containing liquid crystal molecules in a manner that can be easily mass-produced, as well as industrially suitable Periodic Table Group 11 or Group 12. Group metal chalcogenide nanoparticles are provided.
Description
本発明は、周期表第11族又は第12族金属カルコゲナイドナノ粒子及びその製法に関する。周期表第11族又は第12族金属カルコゲナイドナノ粒子は、例えば、液晶ディスプレイの駆動電圧を低下させるための有用な化合物である。 The present invention relates to periodic table group 11 or group 12 metal chalcogenide nanoparticles and a method for producing the same. Group 11 or Group 12 metal chalcogenide nanoparticles of the periodic table are useful compounds for reducing the driving voltage of liquid crystal displays, for example.
従来、周期表第11族金属カルコゲナイド粒子の製法としては、例えば、アルカリ金属及びアルカリ土類金属を除く金属イオンとカルコゲナイド前駆体とを溶解した溶液を超音波処理することにより、金属カルコゲナイドのコロイド粒子を合成する方法が開示されている（例えば、特許文献１参照）。しかしながら、この方法においては、超音波処理のために超音波分散機を使用する必要があり、工業的に大量生産する手法としては不適当であった。又、特許文献１には、周期表第12族金属カルコゲナイドナノ粒子については、実質的には言及されていなかった。
本発明の課題は、上記問題点を解決し、容易に大量製造が可能な方法にて、液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子を提供すること、ならびに工業的に好適な液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子の製法を提供することにある。 An object of the present invention is to provide a periodic table group 11 or group 12 metal chalcogenide nanoparticle containing liquid crystal molecules by a method capable of solving the above problems and easily mass-producing, and industrially. It is an object of the present invention to provide a process for producing Group 11 or Group 12 metal chalcogenide nanoparticles containing suitable liquid crystal molecules.
本発明の課題は、１種又は２種以上の周期表第11族又は第12族金属カルコゲナイド、及び１種又は２種以上の液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子によって解決される。 An object of the present invention is to provide periodic table group 11 or group 12 metal chalcogenide nanoparticles containing one or more group 11 or group 12 metal chalcogenides and one or more liquid crystal molecules. Solved by.
本発明の課題は、又、１種又は２種以上の液晶分子、１種又は２種以上の周期表第11族又は第12族金属塩、及び１又は２種以上のカルコゲナイド前駆体を溶媒中で反応させる、上記の周期表第11族又は第12族金属カルコゲナイドナノ粒子の製法によっても解決される。 Another object of the present invention is to provide one or more liquid crystal molecules, one or two or more periodic table Group 11 or Group 12 metal salts, and one or more chalcogenide precursors in a solvent. This can also be solved by the above-mentioned method for producing Group 11 or Group 12 metal chalcogenide nanoparticles.
本発明により、容易に大量製造が可能な方法にて、液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子を提供することができる。 According to the present invention, Group 11 or Group 12 metal chalcogenide nanoparticles containing liquid crystal molecules can be provided by a method that can be easily mass-produced.
また、工業的に好適な液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子の製法を提供することができる。 In addition, it is possible to provide a method for producing Group 11 or Group 12 metal chalcogenide nanoparticles containing industrially suitable liquid crystal molecules.
本発明の１種又は２種以上の周期表第11族又は第12族金属カルコゲナイド、及び１種又は２種以上の液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子は、例えば、１種又は２種以上の液晶分子、１種又は２種以上の周期表第11族又は第12族金属塩及びカルコゲナイド前駆体とを溶媒中で反応させることによって好適に製造することができる。 The periodic table group 11 or group 12 metal chalcogenide and the periodic table group 11 or group 12 metal chalcogenide nanoparticles containing one or more types of the chalcogenide group 11 or group 12 metal chalcogenide of the present invention, for example, One or two or more liquid crystal molecules, one or two or more periodic table Group 11 or Group 12 metal salts and a chalcogenide precursor can be suitably produced in a solvent.
本発明の反応において使用する液晶分子としては、例えば、4'-n-ペンチル-4-シアノビフェニル、4'-n-ヘキシルオキシ-4-シアノビフェニル等のシアノビフェニル類；4-(trans-4-n-ペンチルシクロヘキシル)ベンゾニトリル等のシクロヘキシルベンゾニトリル類；4'-n-ペンチル-4-エトキシ-2,3-ジフルオロビフェニル、1-エトキシ-2,3-ジフルオロ-4-(trans-4-n-ペンチルシクロヘキシル)ベンゼン等のフルオロベンゼン類；4-ブチル安息香酸(4-シアノフェニル)、4-ヘプチル安息香酸(4-シアノフェニル)等のフェニルエステル類；4-カルボキシフェニルエチルカーボネート、4-カルボキシフェニル-n-ブチルカーボネート等の炭酸エステル類；4-(4-n-ペンチルフェニルエチニル)シアノベンゼン、4-(4-n-ペンチルフェニルエチニル)フルオロベンゼン等のフェニルアセチレン類；2-(4-シアノフェニル)-5-n-ペンチルピリミジン、2-(4-シアノフェニル)-5-n-オクチルピリミジン等のフェニルピリミジン類；4,4'-ビス(エトキシカルボニル)アゾベンゼン等のアゾベンゼン類；4,4’-アゾキシアニソール、4,4'-ジヘキシルアゾキシベンゼン等のアゾキシベンゼン類；N-(4-メトキシベンジリデン)-4-n-ブチルアニリン、N-(4-エトキシベンジリデン)-4-n-ブチルアニリン等のシッフ塩基類；N,N'-ビスベンジリデンベンジジン等のベンジジン類；コレステリルアセテート、コレステリルベンゾエート等のコレステリルエステル類；ポリ(4-フェニレンテレフタルアミド)等の液晶高分子類が挙げられる。なお、これらの液晶分子は、単独又は２種以上を混合して使用しても良く、液晶分子混合物としては、市販品のものをそのまま用いることができる。 Examples of the liquid crystal molecule used in the reaction of the present invention include cyanobiphenyls such as 4′-n-pentyl-4-cyanobiphenyl and 4′-n-hexyloxy-4-cyanobiphenyl; 4- (trans-4 cyclohexylbenzonitriles such as -n-pentylcyclohexyl) benzonitrile; 4'-n-pentyl-4-ethoxy-2,3-difluorobiphenyl, 1-ethoxy-2,3-difluoro-4- (trans-4- fluorobenzenes such as n-pentylcyclohexyl) benzene; phenyl esters such as 4-butylbenzoic acid (4-cyanophenyl) and 4-heptylbenzoic acid (4-cyanophenyl); 4-carboxyphenylethyl carbonate, 4- Carbonates such as carboxyphenyl-n-butyl carbonate; phenylacetylenes such as 4- (4-n-pentylphenylethynyl) cyanobenzene and 4- (4-n-pentylphenylethynyl) fluorobenzene; Phenylpyrimidines such as 2- (4-cyanophenyl) -5-n-pentylpyrimidine and 2- (4-cyanophenyl) -5-n-octylpyrimidine; 4,4′-bis (ethoxycarbonyl) azobenzene and the like Azobenzenes; 4,4'-azoxyanisole, azoxybenzenes such as 4,4'-dihexylazoxybenzene; N- (4-methoxybenzylidene) -4-n-butylaniline, N- (4-ethoxy Schiff bases such as benzylidene) -4-n-butylaniline; benzidines such as N, N'-bisbenzylidenebenzidine; cholesteryl esters such as cholesteryl acetate and cholesteryl benzoate; liquid crystals such as poly (4-phenylene terephthalamide) Examples include polymers. In addition, you may use these liquid crystal molecules individually or in mixture of 2 or more types, and as a liquid crystal molecule mixture, a commercially available thing can be used as it is.
前記液晶分子の使用量は、周期表第11族又は第12族金属塩1モルに対して、好ましくは0.1〜500モル、更に好ましくは1〜200モルである。 The amount of the liquid crystal molecules to be used is preferably 0.1 to 500 mol, more preferably 1 to 200 mol, per 1 mol of the Group 11 or Group 12 metal salt of the periodic table.
本発明の反応において使用する周期表第11族又は第12族金属塩とは、周期表第11族又は第12族金属のイオンと対イオンからなる塩をいう。前記周期表第11族金属のイオンとしては、例えば、Au+、Au3+、Ag+、Cu+、Cu2+からなる群より選ばれる少なくとも１種の金属イオンである。前記周期表第12族金属のイオンとしては、例えば、Zn2+、Cd2+、Hg+、Hg2+からなる群より選ばれる少なくとも１種の金属イオンである。対イオンとしては、例えば、ハロゲンイオン、ハロゲン酸イオン、過ハロゲン酸イオン、置換されていても良いカルボン酸イオン、アセチルアセトナートイオン、炭酸イオン、硫酸イオン、硝酸イオン、テトラフルオロホウ酸イオン、ヘキサフルオロリン酸イオンが挙げられ、周期表第11族金属のイオンの対イオンのときには、ヒドリドイオンも挙げられる。なお、これらの金属塩は、中性の配位子（例えば、一酸化炭素、トリフェニルホスフィン、p-シメン等）が配位していても良い。また、これらの周期表第11族又は第12族金属塩は、単独で又は２種以上を混合して使用しても良い。The group 11 or group 12 metal salt of the periodic table used in the reaction of the present invention refers to a salt comprising a group 11 or group 12 metal ion and a counter ion of the periodic table. The group 11 metal ion of the periodic table is, for example, at least one metal ion selected from the group consisting of Au + , Au 3+ , Ag + , Cu + , and Cu 2+ . The group 12 metal ions in the periodic table are, for example, at least one metal ion selected from the group consisting of Zn 2+ , Cd 2+ , Hg + , and Hg 2+ . Examples of the counter ion include halogen ion, halogen acid ion, perhalogenate ion, optionally substituted carboxylate ion, acetylacetonate ion, carbonate ion, sulfate ion, nitrate ion, tetrafluoroborate ion, hexa Fluorophosphate ions can be mentioned, and in the case of a counter ion of Group 11 metal ions of the periodic table, hydride ions can also be mentioned. These metal salts may be coordinated with a neutral ligand (for example, carbon monoxide, triphenylphosphine, p-cymene, etc.). In addition, these Group 11 or Group 12 metal salts may be used alone or in admixture of two or more.
本発明の反応において使用する周期表第11族又は第12族金属カルコゲナイドとは、周期表第11族又は第12族金属と周期律表の酸素の下の元素（硫黄、セレン、テルル）との化合物を示し、例えば、硫化物、セレン化物、テルル化物が挙げられる。又、カルコゲナイド前駆体とは、例えば、金属化合物（例えば、先に示した金属塩）と反応させることによって、金属カルコゲナイド（例えば、金属硫化物、金属セレン化物、金属テルル化物）を生成する化合物の総称を示す。なお、これらのカルコゲナイド前駆体は、単独で又は金属種の異なる２種以上を混合して使用しても良い。 The periodic table group 11 or group 12 metal chalcogenide used in the reaction of the present invention is a group 11 or group 12 metal of the periodic table and elements under the oxygen of the periodic table (sulfur, selenium, tellurium). Compound, for example, sulfide, selenide, telluride. The chalcogenide precursor is, for example, a compound that forms a metal chalcogenide (for example, metal sulfide, metal selenide, or metal telluride) by reacting with a metal compound (for example, the metal salt shown above). Shows generic name. In addition, you may use these chalcogenide precursors individually or in mixture of 2 or more types from which a metal kind differs.
前記金属硫化物を合成するためのカルコゲナイド前駆体（硫化剤）としては、例えば、チオアセトアミド、N,N-ジメチルチオアセトアミド等のチオアミド類；硫黄；硫化水素；チオ尿素、N,N-ジメチルチオ尿素等のチオ尿素類；硫化ナトリウム、硫化カリウム等のアルカリ金属硫化物類；硫化水素ナトリウム、硫化水素カリウム等のアルカリ金属水素硫化物類が挙げられる。好ましくはチオアミド類、チオ尿素類、アルカリ金属硫化物類、加えて周期律表第12族金属硫化物を合成するときには硫化水素も使用され、更に好ましくはチオアミド類、チオ尿素類、加えて周期律表第12族金属硫化物を合成するときには硫化水素も使用される。なお、これらのカルコゲナイド前駆体（硫化剤）は、単独で又は２種以上を混合して使用しても良い。 Examples of the chalcogenide precursor (sulfurizing agent) for synthesizing the metal sulfide include thioamides such as thioacetamide and N, N-dimethylthioacetamide; sulfur; hydrogen sulfide; thiourea and N, N-dimethylthiourea. Thioureas such as; alkali metal sulfides such as sodium sulfide and potassium sulfide; and alkali metal hydrogen sulfides such as sodium hydrogen sulfide and potassium hydrogen sulfide. Preferably, thioamides, thioureas, alkali metal sulfides, and in addition, hydrogen sulfide is also used when synthesizing group 12 metal sulfides of the periodic table, more preferably thioamides, thioureas, and periodic rules. Hydrogen sulfide is also used when synthesizing Table 12 metal sulfides. In addition, you may use these chalcogenide precursors (sulfurizing agent) individually or in mixture of 2 or more types.
前記金属セレン化物を合成するためのカルコゲナイド前駆体（セレン化剤）としては、例えば、セレン；セレン化水素；セレノアセトアミド、N,N-ジメチルセレノアセトアミド等のセレノアミド類；セレノ尿素、N,N-ジメチルセレノ尿素等のセレノ尿素類；セレン化ナトリウム、セレン化カリウム等のアルカリ金属セレン化物類；セレン化水素ナトリウム、セレン化水素カリウム等のアルカリ金属水素セレン化物類が挙げられる。好ましくはセレン、セレノアミド類、セレノ尿素類、加えて周期律表第12族金属セレン物を合成するときにはセレン化水素も使用され、更に好ましくはセレン、セレノ尿素類、加えて周期律表第12族金属セレン物を合成するときにはセレン化水素も使用される。なお、これらのカルコゲナイド前駆体（セレン化剤）は、単独で又は２種以上を混合して使用しても良い。 Examples of the chalcogenide precursor (selenating agent) for synthesizing the metal selenide include selenium; hydrogen selenide; selenoamides such as selenoacetamide and N, N-dimethylselenoacetamide; selenourea, N, N- Examples include selenoureas such as dimethylselenourea; alkali metal selenides such as sodium selenide and potassium selenide; alkali metal hydrogen selenides such as sodium hydrogen selenide and potassium hydrogen selenide. Preferably, selenium, selenoamides, selenoureas, and also hydrogen selenide is used when synthesizing group 12 metal selenium of the periodic table, more preferably selenium, selenoureas, and group 12 of the periodic table. Hydrogen selenide is also used when synthesizing metal selenides. In addition, you may use these chalcogenide precursors (selenating agent) individually or in mixture of 2 or more types.
前記金属テルル化物を合成するためのカルコゲナイド前駆体（テルル化剤）としては、例えば、テルル；テルル化水素；テルロアセトアミド、N,N-ジメチルテルロアセトアミド等のテルロアミド類；テルロ尿素、N,N-ジメチルテルロ尿素等のテルロ尿素類；テルル化ナトリウム、テルル化カリウム等のアルカリ金属テルル化物類；テルル化水素ナトリウム、テルル化水素カリウム等のアルカリ金属水素テルル化物類が挙げられる。好ましくはテルル、テルロ尿素類、アルカリ金属水素テルル化物類、加えて周期律表第12族金属テルル物を合成するときにはテルル化水素も使用され、更に好ましくはテルル、アルカリ金属水素テルル化物類、加えて周期律表第12族金属テルル物を合成するときにはテルル化水素も使用される。なお、これらのカルコゲナイド前駆体（テルル化剤）は、単独で又は２種以上を混合して使用しても良い。 Examples of the chalcogenide precursor (tellurizing agent) for synthesizing the metal telluride include tellurium; hydrogen telluride; telluramides such as telluroacetamide and N, N-dimethyltelluroacetamide; tellurourea, N, N- Telluroureas such as dimethyltellurourea; alkali metal tellurides such as sodium telluride and potassium telluride; and alkali metal hydrogen tellurides such as sodium telluride and potassium telluride. Preferably tellurium, telluroureas, alkali metal hydrogen tellurides, and also when tellurium group 12 metal tellurides are synthesized, hydrogen telluride is used, more preferably tellurium, alkali metal hydrogen tellurides, addition Thus, when tellurium group 12 metal tellurium is synthesized, hydrogen telluride is also used. These chalcogenide precursors (tellurizing agents) may be used alone or in admixture of two or more.
前記カルコゲナイド前駆体の使用量は、周期表第11族又は第12族金属塩1モルに対して、好ましくは0.1〜5モル、更に好ましくは0.2〜3モルである。 The amount of the chalcogenide precursor used is preferably 0.1 to 5 mol, more preferably 0.2 to 3 mol, per 1 mol of the Group 11 or Group 12 metal salt of the periodic table.
本発明の反応において使用する溶媒としては、反応を阻害しないものならば特に限定されず、例えば、水；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等のエステル類；N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類；N,N'-ジメチルイミダゾリジノン等の尿素類；ジメチルスルホキシド等のスルホキシド類；スルホラン等のスルホン類；アセトニトリル、プロピオニトリル等のニトリル類；ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類；ヘキサン、ヘプタン、シクロヘキサン等の脂肪族炭化水素類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類が挙げられる。好ましくはニトリル類、エーテル類、芳香族炭化水素類、加えて周期律表第11族金属塩のときには水も使用され、更に好ましくはエーテル類、加えて周期律表第11族金属塩のときには水も使用される。なお、これらの溶媒は、単独で又は２種以上を混合して使用しても良い。 The solvent used in the reaction of the present invention is not particularly limited as long as it does not inhibit the reaction. For example, water; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, butyl acetate, propionic acid Esters such as methyl; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Ureas such as N, N′-dimethylimidazolidinone; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Nitriles such as acetonitrile and propionitrile; Ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as hexane, heptane and cyclohexane; Benzene, toluene and xylene Aromatic hydrocarbons That. Preferably, nitriles, ethers, aromatic hydrocarbons, and water in the case of Group 11 metal salts of the periodic table are used, and more preferably ethers, and water in the case of Group 11 metal salts of the periodic table. Also used. In addition, you may use these solvents individually or in mixture of 2 or more types.
前記溶媒の使用量は、液晶分子1gに対して、好ましくは10〜500ml、更に好ましくは20〜200mlである。 The amount of the solvent used is preferably 10 to 500 ml, more preferably 20 to 200 ml, with respect to 1 g of liquid crystal molecules.
本発明の反応は、例えば、１又は２種以上の液晶分子、１又は２種以上の周期表第11族又は第12族金属塩、１又は２種以上のカルコゲナイド前駆体及び溶媒を混合し、場合により加熱しながら攪拌しながら反応させる等の方法によって行われる。その際の反応温度は、好ましくは20〜120℃、更に好ましくは40〜100℃であり、その際の反応圧力は特に制限されない。 The reaction of the present invention includes, for example, mixing one or two or more liquid crystal molecules, one or two or more periodic table Group 11 or Group 12 metal salts, one or two or more chalcogenide precursors, and a solvent. In some cases, the reaction is carried out with stirring while heating. The reaction temperature at that time is preferably 20 to 120 ° C., more preferably 40 to 100 ° C., and the reaction pressure is not particularly limited.
本発明の反応によって周期表第11族金属カルコゲナイドナノ粒子と溶媒とを含む分散液が得られるが、当該分散液を濃縮することによって、均一な周期表第11族又は第12族金属カルコゲナイドナノ粒子と溶媒とを含むペーストを取得することができる。なお、該分散液の濃縮方法は特に限定されないが、減圧下にて、好ましくは20〜100℃にて行うことができる。 According to the reaction of the present invention, a dispersion containing periodic table group 11 metal chalcogenide nanoparticles and a solvent is obtained. By concentrating the dispersion, uniform periodic table group 11 or group 12 metal chalcogenide nanoparticles are obtained. And a solvent containing a solvent can be obtained. The method for concentrating the dispersion is not particularly limited, but can be carried out under reduced pressure, preferably at 20 to 100 ° C.
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
実施例１（硫化銀ナノ粒子の合成）
攪拌装置、温度計及び還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン45.0ml、水0.05ml及び0.01mol/lチオアセトアミドのテトラヒドロフラン溶液1.65ml(0.0165mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/lトリフルオロ酢酸銀のテトラヒドロフラン溶液3.30ml(銀原子として0.033mmol)をゆるやかに滴下し反応させた。反応終了後、反応液を室温まで冷却し、茶褐色の均一な液体として、硫化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化銀ナノ粒子の粒径は10〜30nmで均一であった（図１）。更に、得られた硫化銀ナノ粒子を含む分散液を減圧下で濃縮し、茶褐色の均一な硫化銀ナノ粒子ペースト0.67gを取得した。Example 1 (Synthesis of silver sulfide nanoparticles)
In a glass container having an internal volume of 100 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.66 g (2.64 mmol) of 4′-n-pentyl-4-cyanobiphenyl, 45.0 ml of tetrahydrofuran, 0.05 ml of water and 0.01 mol / l 1.65 ml (0.0165 mmol) of a tetrahydrofuran solution of thioacetamide was added, and the mixed solution was heated to 65 to 75 ° C. with stirring. Next, 3.30 ml of 0.01 mol / l silver trifluoroacetate tetrahydrofuran solution (0.033 mmol as silver atoms) was gently added dropwise to react. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 50 ml of a silver sulfide nanoparticle dispersion as a brownish brown uniform liquid. As a result of analysis with a transmission electron microscope, the particle size of the silver sulfide nanoparticles was uniform at 10 to 30 nm (FIG. 1). Furthermore, the obtained dispersion containing silver sulfide nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a brownish brown uniform silver sulfide nanoparticle paste.
実施例２（硫化銀ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン45.0ml、水0.05ml及び0.01mol/lチオアセトアミドのテトラヒドロフラン溶液1.65ml(0.0165mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/l過塩素酸銀のテトラヒドロフラン溶液3.30ml(銀原子として0.033mmol)をゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、茶褐色の均一な液体として、硫化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化銀ナノ粒子の粒径は10〜30nmで均一であった（図２）。更に、得られた硫化銀ナノ粒子を含む分散液を減圧下で濃縮し、茶褐色の均一な硫化銀ナノ粒子ペースト0.67gを取得した。Example 2 (Synthesis of silver sulfide nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer, reflux condenser, 4'-n-pentyl-4-cyanobiphenyl 0.66 g (2.64 mmol), tetrahydrofuran 45.0 ml, water 0.05 ml and 0.01 mol / l 1.65 ml (0.0165 mmol) of a tetrahydrofuran solution of thioacetamide was added, and the mixed solution was heated to 65 to 75 ° C. with stirring. Next, 3.30 ml (0.033 mmol as silver atoms) of a 0.01 mol / l silver perchlorate tetrahydrofuran solution was gently added dropwise to cause the reaction. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a silver sulfide nanoparticle dispersion as a brownish brown uniform liquid. As a result of analysis with a transmission electron microscope, the silver sulfide nanoparticles had a uniform particle size of 10 to 30 nm (FIG. 2). Furthermore, the obtained dispersion containing silver sulfide nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a brownish brown uniform silver sulfide nanoparticle paste.
実施例３（硫化銅ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン43.4ml、水0.05ml及び0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.30ml(0.033mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/lトリフルオロ酢酸銅(II)のテトラヒドロフラン溶液3.30ml(銅原子として0.033mmol)をゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、茶褐色の均一な液体として、硫化銅ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化銅ナノ粒子の粒径は2nm程度で均一であった(図３)。更に、得られた硫化銅ナノ粒子を含む分散液を減圧下で濃縮し、茶褐色の均一な硫化銅ナノ粒子ペースト0.67gを取得した。Example 3 (Synthesis of copper sulfide nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer, reflux condenser, 4'-n-pentyl-4-cyanobiphenyl 0.66 g (2.64 mmol), tetrahydrofuran 43.4 ml, water 0.05 ml and 0.01 mol / l A solution of thioacetamide in tetrahydrofuran (3.30 ml, 0.033 mmol) was added and the mixture was heated to 65-75 ° C. with stirring. Next, 3.30 ml (0.033 mmol as a copper atom) of a tetrahydrofuran solution of 0.01 mol / l copper trifluoroacetate (II) was slowly dropped and reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a copper sulfide nanoparticle dispersion as a brownish brown uniform liquid. As a result of analysis with a transmission electron microscope, the copper sulfide nanoparticles had a uniform particle size of about 2 nm (FIG. 3). Furthermore, the obtained dispersion liquid containing copper sulfide nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a brownish brown uniform copper sulfide nanoparticle paste.
実施例４（硫化銅ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン43.4ml、水0.05ml及び0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.30ml(0.033mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/l酢酸銅(II)のテトラヒドロフラン溶液3.30ml(銅原子として0.033mmol)をゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、茶褐色の均一な液体として、硫化銅ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化銅ナノ粒子の粒径は10〜30nmで均一であった(図４)。更に、得られた硫化銅ナノ粒子を含む分散液を減圧下で濃縮し、茶褐色の均一な硫化銅ナノ粒子ペースト0.67gを取得した。Example 4 (Synthesis of copper sulfide nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer, reflux condenser, 4'-n-pentyl-4-cyanobiphenyl 0.66 g (2.64 mmol), tetrahydrofuran 43.4 ml, water 0.05 ml and 0.01 mol / l A solution of thioacetamide in tetrahydrofuran (3.30 ml, 0.033 mmol) was added and the mixture was heated to 65-75 ° C. with stirring. Next, 3.30 ml (0.033 mmol as a copper atom) of a tetrahydrofuran solution of 0.01 mol / l copper acetate (II) was slowly dropped and reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a copper sulfide nanoparticle dispersion as a brownish brown uniform liquid. As a result of analysis with a transmission electron microscope, the copper sulfide nanoparticles had a uniform particle size of 10 to 30 nm (FIG. 4). Furthermore, the obtained dispersion liquid containing copper sulfide nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a brownish brown uniform copper sulfide nanoparticle paste.
実施例５（硫化銅ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン43.4ml、水0.05ml及び0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.30ml(0.033mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/l銅(II)アセチルアセトナートのテトラヒドロフラン溶液3.30ml(銅原子として0.033mmol)をゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、茶褐色の均一な液体として、硫化銅ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化銅ナノ粒子の粒径は2nm程度で均一であった（図５）。更に、得られた硫化銅ナノ粒子を含む分散液を減圧下で濃縮し、茶褐色の均一な硫化銅ナノ粒子ペースト0.67gを取得した。Example 5 (Synthesis of copper sulfide nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer, reflux condenser, 4'-n-pentyl-4-cyanobiphenyl 0.66 g (2.64 mmol), tetrahydrofuran 43.4 ml, water 0.05 ml and 0.01 mol / l A solution of thioacetamide in tetrahydrofuran (3.30 ml, 0.033 mmol) was added and the mixture was heated to 65-75 ° C. with stirring. Next, 3.30 ml of 0.01 mol / l copper (II) acetylacetonate in tetrahydrofuran (0.033 mmol as copper atoms) was slowly added dropwise to cause the reaction. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a copper sulfide nanoparticle dispersion as a brownish brown uniform liquid. As a result of analysis with a transmission electron microscope, the copper sulfide nanoparticles had a uniform particle size of about 2 nm (FIG. 5). Furthermore, the obtained dispersion liquid containing copper sulfide nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a brownish brown uniform copper sulfide nanoparticle paste.
実施例６（硫化銅ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン43.4ml、水0.05ml及び0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.30ml(0.033mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/lテトラフルオロホウ酸銅(II)のテトラヒドロフラン溶液3.30ml(銅原子として0.033mmol)をゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、茶褐色の均一な液体として、硫化銅ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化銅ナノ粒子の粒径は2nm程度で均一であった（図６)。更に、得られた硫化銅ナノ粒子を含む分散液を減圧下で濃縮し、茶褐色の均一な硫化銅ナノ粒子ペースト0.67gを取得した。Example 6 (Synthesis of copper sulfide nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer, reflux condenser, 4'-n-pentyl-4-cyanobiphenyl 0.66 g (2.64 mmol), tetrahydrofuran 43.4 ml, water 0.05 ml and 0.01 mol / l A solution of thioacetamide in tetrahydrofuran (3.30 ml, 0.033 mmol) was added and the mixture was heated to 65-75 ° C. with stirring. Next, 3.30 ml (0.033 mmol as a copper atom) of a tetrahydrofuran solution of 0.01 mol / l copper (II) tetrafluoroborate was slowly dropped and reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a copper sulfide nanoparticle dispersion as a brownish brown uniform liquid. As a result of analysis with a transmission electron microscope, the copper sulfide nanoparticles had a uniform particle size of about 2 nm (FIG. 6). Furthermore, the obtained dispersion liquid containing copper sulfide nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a brownish brown uniform copper sulfide nanoparticle paste.
実施例７（テルル化銀ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン43.4ml及びテルル4.2mg(0.033mmol)を加え、次いで、0.01mol/lトリフルオロ酢酸銀のテトラヒドロフラン溶液6.60ml(銀原子として0.066mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、灰白色の均一な液体として、テルル化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化銀ナノ粒子の粒径は3〜15nmで均一であった(図７)。更に、得られたテルル化銀ナノ粒子を含む分散液を減圧下で濃縮し、灰白色の均一なテルル化銀ナノ粒子ペースト0.67gを取得した。Example 7 (Synthesis of silver telluride nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer, reflux condenser, 4'-n-pentyl-4-cyanobiphenyl 0.66 g (2.64 mmol), tetrahydrofuran 43.4 ml and tellurium 4.2 mg (0.033 mmol) Then, 6.60 ml of 0.01 mol / l silver trifluoroacetate in tetrahydrofuran (0.066 mmol as silver atoms) was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of silver telluride nanoparticle dispersion as an off-white uniform liquid. As a result of analysis with a transmission electron microscope, the silver telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 7). Further, the obtained dispersion containing silver telluride nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a grayish white uniform silver telluride nanoparticle paste.
実施例８（テルル化銀ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（ZLI-5100-100（メルク社製））0.50g、テトラヒドロフラン44.0ml及びテルル3.8mg(0.030mmol)を加え、次いで、0.01mol/lトリフルオロ酢酸銀のテトラヒドロフラン溶液6.00ml(銀原子として0.060mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、灰白色の均一な液体として、テルル化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化銀ナノ粒子の粒径は3〜15nmで均一であった(図８)。更に、得られたテルル化銀ナノ粒子を含む分散液を減圧下で濃縮し、灰白色の均一なテルル化銀ナノ粒子ペースト0.51gを取得した。Example 8 (Synthesis of silver telluride nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (ZLI-5100-100 (Merck)), 44.0 ml of tetrahydrofuran and 3.8 mg of tellurium (0.030 mmol) Then, 6.00 ml (0.060 mmol as silver atoms) of 0.01 mol / l silver trifluoroacetate in tetrahydrofuran was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of silver telluride nanoparticle dispersion as an off-white uniform liquid. As a result of analysis with a transmission electron microscope, the silver telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 8). Further, the obtained dispersion liquid containing silver telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a grayish white uniform silver telluride nanoparticle paste.
実施例９（テルル化銀ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6054-100（メルク社製））0.50g、テトラヒドロフラン44.0ml及びテルル3.8mg(0.030mmol)を加え、次いで、0.01mol/lトリフルオロ酢酸銀のテトラヒドロフラン溶液6.00ml(銀原子として0.060mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、灰白色の均一な液体として、テルル化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化銀ナノ粒子の粒径は3〜15nmで均一であった(図９)。更に、得られたテルル化銀ナノ粒子を含む分散液を減圧下で濃縮し、灰白色の均一なテルル化銀ナノ粒子ペースト0.51gを取得した。Example 9 (Synthesis of silver telluride nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6054-100 (Merck)), 44.0 ml of tetrahydrofuran and 3.8 mg of tellurium (0.030 mmol) Then, 6.00 ml (0.060 mmol as silver atoms) of 0.01 mol / l silver trifluoroacetate in tetrahydrofuran was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of silver telluride nanoparticle dispersion as an off-white uniform liquid. As a result of analysis with a transmission electron microscope, the silver telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 9). Further, the obtained dispersion liquid containing silver telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a grayish white uniform silver telluride nanoparticle paste.
実施例１０（テルル化銀ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6292-100（メルク社製））0.50g、テトラヒドロフラン44.0ml及びテルル3.8mg(0.030mmol)を加え、次いで、0.01mol/lトリフルオロ酢酸銀のテトラヒドロフラン溶液6.00ml(銀原子として0.060mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、灰白色の均一な液体として、テルル化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化銀ナノ粒子の粒径は3〜15nmで均一であった(図１０)。更に、得られたテルル化銀ナノ粒子を含む分散液を減圧下で濃縮し、灰白色の均一なテルル化銀ナノ粒子ペースト0.51gを取得した。Example 10 (Synthesis of silver telluride nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6292-100 (Merck)), 44.0 ml of tetrahydrofuran and 3.8 mg of tellurium (0.030 mmol) Then, 6.00 ml (0.060 mmol as silver atoms) of 0.01 mol / l silver trifluoroacetate in tetrahydrofuran was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of silver telluride nanoparticle dispersion as an off-white uniform liquid. As a result of analysis with a transmission electron microscope, the silver telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 10). Further, the obtained dispersion liquid containing silver telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a grayish white uniform silver telluride nanoparticle paste.
実施例１１（テルル化銀ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6608（メルク社製））0.50g、テトラヒドロフラン44.0ml及びテルル3.8mg(0.030mmol)を加え、次いで、0.01mol/lトリフルオロ酢酸銀のテトラヒドロフラン溶液6.00ml(銀原子として0.060mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、灰白色の均一な液体として、テルル化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化銀ナノ粒子の粒径は3〜15nmで均一であった(図１１)。更に、得られたテルル化銀ナノ粒子を含む分散液を減圧下で濃縮し、灰白色の均一なテルル化銀ナノ粒子ペースト0.51gを取得した。Example 11 (Synthesis of silver telluride nanoparticles)
Add 0.50 g of liquid crystal molecule mixture (MLC-6608 (Merck)), 44.0 ml of tetrahydrofuran and 3.8 mg (0.030 mmol) of tellurium to a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer and reflux condenser. Next, 6.00 ml of 0.01 mol / l silver trifluoroacetate in tetrahydrofuran (0.060 mmol as silver atoms) was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of silver telluride nanoparticle dispersion as an off-white uniform liquid. As a result of analysis with a transmission electron microscope, the silver telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 11). Further, the obtained dispersion liquid containing silver telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a grayish white uniform silver telluride nanoparticle paste.
実施例１２（テルル化銀ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6692（メルク社製））0.50g、テトラヒドロフラン44.0ml及びテルル3.8mg(0.030mmol)を加え、次いで、0.01mol/lトリフルオロ酢酸銀のテトラヒドロフラン溶液6.00ml(銀原子として0.060mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、灰白色の均一な液体として、テルル化銀ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化銀ナノ粒子の粒径は3〜15nmで均一であった(図１２)。更に、得られたテルル化銀ナノ粒子を含む分散液を減圧下で濃縮し、灰白色の均一なテルル化銀ナノ粒子ペースト0.51gを取得した。Example 12 (Synthesis of silver telluride nanoparticles)
Add 0.50 g of liquid crystal molecule mixture (MLC-6692 (Merck)), 44.0 ml of tetrahydrofuran and 3.8 mg (0.030 mmol) of tellurium to a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer and reflux condenser. Next, 6.00 ml of 0.01 mol / l silver trifluoroacetate in tetrahydrofuran (0.060 mmol as silver atoms) was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of silver telluride nanoparticle dispersion as an off-white uniform liquid. As a result of analysis with a transmission electron microscope, the silver telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 12). Further, the obtained dispersion liquid containing silver telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a grayish white uniform silver telluride nanoparticle paste.
実施例１３（硫化カドミウムナノ粒子の合成）
攪拌装置、温度計及び還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.70g(2.81mmol)、テトラヒドロフラン46.3ml、水0.05ml及びカドミウムアセチルアセトナート11.5mg（0.037mmol）を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.70mlをゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、淡黄色の均一な液体として、硫化カドミウムナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化亜鉛ナノ粒子の粒径は5〜10nmで均一であった（図１３）。更に、得られた硫化カドミウムナノ粒子を含む分散液を減圧下で濃縮し、淡黄色の均一な硫化亜鉛ナノ粒子ペースト0.71gを取得した。Example 13 (Synthesis of cadmium sulfide nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.70 g (2.81 mmol) of 4′-n-pentyl-4-cyanobiphenyl, 46.3 ml of tetrahydrofuran, 0.05 ml of water and cadmium acetylacetate 11.5 mg (0.037 mmol) of natto was added and the mixture was heated to 65-75 ° C. with stirring. Subsequently, 3.70 ml of a 0.01 mol / l thioacetamide tetrahydrofuran solution was gently dropped and reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a cadmium sulfide nanoparticle dispersion as a pale yellow uniform liquid. As a result of analysis with a transmission electron microscope, the particle size of the zinc sulfide nanoparticles was uniform at 5 to 10 nm (FIG. 13). Further, the obtained dispersion liquid containing cadmium sulfide nanoparticles was concentrated under reduced pressure to obtain 0.71 g of a pale yellow uniform zinc sulfide nanoparticle paste.
実施例１４（硫化亜鉛ナノ粒子の合成）
攪拌装置、温度計及び還流冷却器を備えた内容積100mlのガラス製容器に、4'-n-ペンチル-4-シアノビフェニル0.66g(2.64mmol)、テトラヒドロフラン43.4ml、水0.05ml及び0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.30mlを加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/l亜鉛アセチルアセトナートのテトラヒドロフラン溶液3.30ml(亜鉛原子として0.033mmol)をゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、硫化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化亜鉛ナノ粒子の粒径は2〜10nmで均一であった（図１４）。更に、得られた硫化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、淡黄色の均一な硫化亜鉛ナノ粒子ペースト0.67gを取得した。Example 14 (Synthesis of zinc sulfide nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, a thermometer and a reflux condenser, 4'-n-pentyl-4-cyanobiphenyl 0.66 g (2.64 mmol), tetrahydrofuran 43.4 ml, water 0.05 ml and 0.01 mol / l 3.30 ml of a tetrahydrofuran solution of thioacetamide was added, and the mixed solution was heated to 65 to 75 ° C. with stirring. Next, 3.30 ml of 0.01 mol / l zinc acetylacetonate in tetrahydrofuran (0.033 mmol as zinc atoms) was gently added dropwise to cause the reaction. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a zinc sulfide nanoparticle dispersion as a colorless uniform liquid. As a result of analysis with a transmission electron microscope, the zinc sulfide nanoparticles had a uniform particle size of 2 to 10 nm (FIG. 14). Further, the obtained dispersion containing zinc sulfide nanoparticles was concentrated under reduced pressure to obtain 0.67 g of a pale yellow uniform zinc sulfide nanoparticle paste.
実施例１５（硫化亜鉛ナノ粒子の合成）
攪拌装置、温度計及び還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6692（メルク社製））0.50g、テトラヒドロフラン47ml、水0.05ml及び亜鉛アセチルアセトナート7.8mg（0.03mmol）を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.0mlをゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、硫化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化亜鉛ナノ粒子の粒径は2〜10nmで均一であった（図１５）。更に、得られた硫化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、淡黄色の均一な硫化亜鉛ナノ粒子ペースト0.50gを取得した。Example 15 (Synthesis of zinc sulfide nanoparticles)
In a 100 ml glass container equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6692 (Merck)), 47 ml of tetrahydrofuran, 0.05 ml of water and 7.8 mg of zinc acetylacetonate (0.03 mmol) was added and the mixture was heated to 65-75 ° C. with stirring. Next, 3.0 ml of a 0.01 mol / l thioacetamide tetrahydrofuran solution was slowly dropped and reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a zinc sulfide nanoparticle dispersion as a colorless uniform liquid. As a result of analysis with a transmission electron microscope, the zinc sulfide nanoparticles had a uniform particle size of 2 to 10 nm (FIG. 15). Further, the obtained dispersion containing zinc sulfide nanoparticles was concentrated under reduced pressure to obtain 0.50 g of a pale yellow uniform zinc sulfide nanoparticle paste.
実施例１６（硫化亜鉛ナノ粒子の合成）
攪拌装置、温度計及び還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6608（メルク社製））0.50g、テトラヒドロフラン47ml、水0.05ml及び亜鉛アセチルアセトナート7.8mg（0.03mmol）を加え、当該混合溶液を攪拌しながら65〜75℃に加熱した。次いで、0.01mol/lチオアセトアミドのテトラヒドロフラン溶液3.0mlをゆるやかに滴下し反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、硫化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、硫化亜鉛ナノ粒子の粒径は2〜10nmで均一であった（図１６）。更に、得られた硫化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、淡黄色の均一な硫化亜鉛ナノ粒子ペースト0.50gを取得した。Example 16 (Synthesis of zinc sulfide nanoparticles)
In a 100 ml glass container equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6608 (Merck)), 47 ml of tetrahydrofuran, 0.05 ml of water and 7.8 mg of zinc acetylacetonate (0.03 mmol) was added and the mixture was heated to 65-75 ° C. with stirring. Next, 3.0 ml of a 0.01 mol / l thioacetamide tetrahydrofuran solution was slowly dropped and reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of a zinc sulfide nanoparticle dispersion as a colorless uniform liquid. As a result of analysis with a transmission electron microscope, the particle size of the zinc sulfide nanoparticles was uniform at 2 to 10 nm (FIG. 16). Further, the obtained dispersion containing zinc sulfide nanoparticles was concentrated under reduced pressure to obtain 0.50 g of a pale yellow uniform zinc sulfide nanoparticle paste.
実施例１７（テルル化亜鉛ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（ZLI-5100-100（メルク社製））0.50g、テトラヒドロフラン44.0ml、亜鉛アセチルアセトナート8.1mg(0.030mmol)、次いで、テルル3.8mg(0.030mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、テルル化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化亜鉛ナノ粒子の粒径は3〜15nmで均一であった(図１７)。更に、得られたテルル化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、無色の均一なテルル化亜鉛ナノ粒子ペースト0.51gを取得した。Example 17 (Synthesis of zinc telluride nanoparticles)
In a 100 ml glass container equipped with a stirrer, thermometer, reflux condenser, 0.50 g liquid crystal molecule mixture (ZLI-5100-100 (Merck)), 44.0 ml tetrahydrofuran, 8.1 mg zinc acetylacetonate ( 0.030 mmol) and then 3.8 mg (0.030 mmol) of tellurium were added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of zinc telluride nanoparticle dispersion as a colorless and uniform liquid. As a result of analysis with a transmission electron microscope, the zinc telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 17). Further, the obtained dispersion containing zinc telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a colorless uniform zinc telluride nanoparticle paste.
実施例１８（テルル化亜鉛ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6054-100（メルク社製））0.50g、テトラヒドロフラン44.0ml、亜鉛アセチルアセトナート8.1mg(0.030mmol)、次いで、テルル3.8mg(0.030mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、テルル化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化亜鉛ナノ粒子の粒径は3〜15nmで均一であった(図１８)。更に、得られたテルル化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、無色の均一なテルル化亜鉛ナノ粒子ペースト0.51gを取得した。Example 18 (Synthesis of zinc telluride nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6054-100 (Merck)), 44.0 ml of tetrahydrofuran, 8.1 mg of zinc acetylacetonate ( 0.030 mmol) and then 3.8 mg (0.030 mmol) of tellurium were added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of zinc telluride nanoparticle dispersion as a colorless and uniform liquid. As a result of analysis with a transmission electron microscope, the zinc telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 18). Further, the obtained dispersion containing zinc telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a colorless uniform zinc telluride nanoparticle paste.
実施例１９（テルル化亜鉛ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6292-100（メルク社製））0.50g、テトラヒドロフラン44.0ml、亜鉛アセチルアセトナート8.1mg(0.030mmol)、次いで、テルル3.8mg(0.030mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、テルル化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化亜鉛ナノ粒子の粒径は3〜15nmで均一であった(図１９)。更に、得られたテルル化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、無色の均一なテルル化亜鉛ナノ粒子ペースト0.51gを取得した。Example 19 (Synthesis of zinc telluride nanoparticles)
In a 100 ml glass container equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6292-100 (Merck)), 44.0 ml of tetrahydrofuran, 8.1 mg of zinc acetylacetonate ( 0.030 mmol) and then 3.8 mg (0.030 mmol) of tellurium were added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of zinc telluride nanoparticle dispersion as a colorless and uniform liquid. As a result of analysis with a transmission electron microscope, the zinc telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 19). Further, the obtained dispersion containing zinc telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a colorless uniform zinc telluride nanoparticle paste.
実施例２０（テルル化亜鉛ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6608（メルク社製））0.50g、テトラヒドロフラン44.0ml、亜鉛アセチルアセトナート8.1mg(0.030mmol)、次いで、テルル3.8mg(0.030mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、テルル化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化亜鉛ナノ粒子の粒径は3〜15nmで均一であった(図２０)。更に、得られたテルル化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、無色の均一なテルル化亜鉛ナノ粒子ペースト0.51gを取得した。Example 20 (Synthesis of zinc telluride nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer, reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6608 (Merck)), 44.0 ml of tetrahydrofuran, 8.1 mg (0.030 mmol) of zinc acetylacetonate Then, 3.8 mg (0.030 mmol) of tellurium was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of zinc telluride nanoparticle dispersion as a colorless and uniform liquid. As a result of analysis with a transmission electron microscope, the particle size of the zinc telluride nanoparticles was uniform at 3 to 15 nm (FIG. 20). Further, the obtained dispersion containing zinc telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a colorless uniform zinc telluride nanoparticle paste.
実施例２１（テルル化亜鉛ナノ粒子の合成）
攪拌装置、温度計、還流冷却器を備えた内容積100mlのガラス製容器に、液晶分子混合物（MLC-6692（メルク社製））0.50g、テトラヒドロフラン44.0ml、亜鉛アセチルアセトナート8.1mg(0.030mmol)、次いで、テルル3.8mg(0.030mmol)を加え、当該混合溶液を攪拌しながら65〜75℃に加熱し、反応させた。反応終了後、混合物を室温まで冷却し、無色の均一な液体として、テルル化亜鉛ナノ粒子分散液50mlを得た。これを透過型電子顕微鏡により分析した結果、テルル化亜鉛ナノ粒子の粒径は3〜15nmで均一であった(図２１)。更に、得られたテルル化亜鉛ナノ粒子を含む分散液を減圧下で濃縮し、無色の均一なテルル化亜鉛ナノ粒子ペースト0.51gを取得した。Example 21 (Synthesis of zinc telluride nanoparticles)
In a glass container with an internal volume of 100 ml equipped with a stirrer, thermometer and reflux condenser, 0.50 g of liquid crystal molecule mixture (MLC-6692 (Merck)), 44.0 ml of tetrahydrofuran, 8.1 mg (0.030 mmol) of zinc acetylacetonate Then, 3.8 mg (0.030 mmol) of tellurium was added, and the mixed solution was heated to 65 to 75 ° C. with stirring to be reacted. After completion of the reaction, the mixture was cooled to room temperature to obtain 50 ml of zinc telluride nanoparticle dispersion as a colorless and uniform liquid. As a result of analysis with a transmission electron microscope, the zinc telluride nanoparticles had a uniform particle size of 3 to 15 nm (FIG. 21). Further, the obtained dispersion containing zinc telluride nanoparticles was concentrated under reduced pressure to obtain 0.51 g of a colorless uniform zinc telluride nanoparticle paste.
本発明は、液晶分子を含む周期表第11族又は第12族金属カルコゲナイドナノ粒子及びその製法に関する。周期表第11族又は第12族金属カルコゲナイドナノ粒子は、例えば、液晶ディスプレイの駆動電圧を低下させるための有用な化合物である。 The present invention relates to Periodic Table Group 11 or Group 12 metal chalcogenide nanoparticles containing liquid crystal molecules and a method for producing the same. Group 11 or Group 12 metal chalcogenide nanoparticles of the periodic table are useful compounds for reducing the driving voltage of liquid crystal displays, for example.
Claims (10)
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| JP2008526824A Expired - Fee Related JP5332612B2 (en) | 2006-07-27 | 2007-07-27 | Method for producing periodic table group 11 or group 12 metal chalcogenide nanoparticles |
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| JP (1) | JP5332612B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011522787A (en) * | 2008-04-28 | 2011-08-04 | ナンジェネックス ナノテクノロジー インコーポレイテッド | Instrumentation and process for producing nanoparticles in continuous flow mode |
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| JP2009249469A (en) * | 2008-04-04 | 2009-10-29 | Ube Ind Ltd | Liquid crystal material containing metal chalcogenide nanoparticle, and liquid crystal display device comprising the same |
| JP2011011956A (en) * | 2009-07-03 | 2011-01-20 | Teijin Ltd | Chalcopyrite type fine particle and production method thereof |
| JP2012076976A (en) * | 2010-10-06 | 2012-04-19 | National Institute For Materials Science | Method for synthesizing powders of sulfide and selenide |
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| JP4104892B2 (en) * | 2001-08-31 | 2008-06-18 | 直樹 戸嶋 | Liquid crystal display |
| JP3701622B2 (en) * | 2002-03-27 | 2005-10-05 | 日立ソフトウエアエンジニアリング株式会社 | Semiconductor nanoparticle fluorescent reagent and fluorescence measuring method |
| JP4392186B2 (en) * | 2003-04-14 | 2009-12-24 | 大日本印刷株式会社 | High-speed response liquid crystal device and driving method |
| JP2006291016A (en) * | 2005-04-08 | 2006-10-26 | Nano Opt Kenkyusho:Kk | Liquid crystal compatible nanorod, method for producing the same, liquid crystal medium, and liquid crystal element |
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| JP2011522787A (en) * | 2008-04-28 | 2011-08-04 | ナンジェネックス ナノテクノロジー インコーポレイテッド | Instrumentation and process for producing nanoparticles in continuous flow mode |
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| TW200811051A (en) | 2008-03-01 |
| JP5332612B2 (en) | 2013-11-06 |
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