JP2017132848A - Method for producing carbon-based light emitting material - Google Patents
Method for producing carbon-based light emitting material Download PDFInfo
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- JP2017132848A JP2017132848A JP2016012231A JP2016012231A JP2017132848A JP 2017132848 A JP2017132848 A JP 2017132848A JP 2016012231 A JP2016012231 A JP 2016012231A JP 2016012231 A JP2016012231 A JP 2016012231A JP 2017132848 A JP2017132848 A JP 2017132848A
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- carbon
- luminescent material
- based luminescent
- acid
- producing
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Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
本発明は、炭素系発光材料の製造方法に関する。 The present invention relates to a method for producing a carbon-based luminescent material.
近年、発光材料として、炭素系発光材料が注目されている。炭素系発光材料の一例として、グラフェン量子ドットが挙げられる。グラフェン量子ドットは、半導体量子ドットに比べて、価格、安全性、化学的安定性等の点で優位性が期待されているが、肝心の発光特性は、現在のところ半導体量子ドットの方が優れている。グラフェン量子ドットの利点を生かして次世代発光体として用いるためには、光学的な特性を改善する必要がある。 In recent years, carbon-based light emitting materials have attracted attention as light emitting materials. An example of the carbon-based luminescent material is graphene quantum dots. Graphene quantum dots are expected to have advantages over semiconductor quantum dots in terms of price, safety, chemical stability, etc., but semiconductor quantum dots are currently superior in light emission characteristics. ing. In order to utilize the advantage of graphene quantum dots as a next-generation light emitter, it is necessary to improve optical characteristics.
本発明は、前記事情に鑑みなされたもので、量子収率が向上し、優れた発光特性を有する炭素系発光材料の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a carbon-based light emitting material having an improved quantum yield and excellent light emission characteristics.
本発明者らは、前記目的を達成するために鋭意検討を重ねた結果、多価カルボン酸を含む原料、酸触媒及び溶媒を混合して加熱することで得られる炭素系発光材料を還元剤で処理することによって、該炭素系発光材料の量子収率を向上させることができることを見出し、本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventors have obtained a carbon-based luminescent material obtained by mixing and heating a raw material containing a polyvalent carboxylic acid, an acid catalyst and a solvent with a reducing agent. It has been found that the quantum yield of the carbon-based luminescent material can be improved by the treatment, and the present invention has been completed.
すなわち、本発明は、下記炭素系発光材料の製造方法を提供する。
１．多価カルボン酸を含む原料、酸触媒及び溶媒を混合して、加熱して炭素系発光材料を製造する工程、及び
前記工程で得られた炭素系発光材料を、還元剤を用いて還元処理する工程
を含む炭素系発光材料の製造方法。
２．前記還元剤が、水素化ホウ素ナトリウムである１の炭素系発光材料の製造方法。
３．前記多価カルボン酸が、クエン酸である１又は２の炭素系発光材料の製造方法。
４．前記原料が、更に、アミノ基含有化合物を含む１〜３のいずれかの炭素系発光材料の製造方法。
５．前記アミノ基含有化合物が、アミノ酸である４の炭素系発光材料の製造方法。
６．前記アミノ酸が、グリシンである５の炭素系発光材料の製造方法。
７．前記酸触媒が、細孔を有する多孔質体不均一酸触媒である１〜６のいずれかの炭素系発光材料の製造方法。
８．前記炭素系発光材料がグラフェン構造を有するものである１〜７のいずれかの炭素系発光材料の製造方法。
９．前記炭素系発光材料が、波長２００〜３８０ｎｍの励起光によって波長３８０〜４８０ｎｍの光を発するものである１〜８のいずれかの炭素系発光材料の製造方法。
１０．多価カルボン酸を含む原料、酸触媒及び溶媒を混合して、加熱して得られる炭素系発光材料を還元剤で処理する、炭素系発光材料の量子収率を向上させる方法。
That is, this invention provides the manufacturing method of the following carbon-type luminescent material.
1. A step of mixing a raw material containing a polyvalent carboxylic acid, an acid catalyst and a solvent and heating to produce a carbon-based luminescent material, and a reduction treatment of the carbon-based luminescent material obtained in the step using a reducing agent The manufacturing method of the carbon-type luminescent material including a process.
2. The method for producing a carbon-based luminescent material according to claim 1, wherein the reducing agent is sodium borohydride.
3. The manufacturing method of the 1 or 2 carbon type luminescent material whose said polyhydric carboxylic acid is a citric acid.
4). The method for producing a carbon-based light-emitting material according to any one of 1 to 3, wherein the raw material further contains an amino group-containing compound.
5. A method for producing a carbon-based luminescent material of 4, wherein the amino group-containing compound is an amino acid.
6). A method for producing a carbon-based luminescent material according to 5, wherein the amino acid is glycine.
7). The method for producing a carbon-based luminescent material according to any one of 1 to 6, wherein the acid catalyst is a porous heterogeneous acid catalyst having pores.
8). The method for producing a carbon-based light-emitting material according to any one of 1 to 7, wherein the carbon-based light-emitting material has a graphene structure.
9. The method for producing a carbon-based luminescent material according to any one of 1 to 8, wherein the carbon-based luminescent material emits light having a wavelength of 380 to 480 nm by excitation light having a wavelength of 200 to 380 nm.
10. A method for improving the quantum yield of a carbon-based luminescent material, comprising mixing a raw material containing a polyvalent carboxylic acid, an acid catalyst, and a solvent, and treating the carbon-based luminescent material obtained by heating with a reducing agent.
本発明の炭素系発光材料の製造方法によれば、量子収率が向上し、優れた発光特性を有する炭素系発光材料を製造することができる。 According to the method for producing a carbon-based light-emitting material of the present invention, a carbon-based light-emitting material having improved quantum yield and excellent light emission characteristics can be produced.
本発明の炭素系発光材料の製造方法は、多価カルボン酸を含む原料、酸触媒及び溶媒を混合して、加熱して炭素系発光材料を製造する工程（以下、工程１という。）、及び前記工程で得られた炭素系発光材料を、還元剤を用いて還元処理する工程（以下、工程２という。）を含むものである。 In the method for producing a carbon-based luminescent material of the present invention, a raw material containing a polyvalent carboxylic acid, an acid catalyst, and a solvent are mixed and heated to produce a carbon-based luminescent material (hereinafter referred to as step 1), and It includes a step of reducing the carbon-based light emitting material obtained in the above step using a reducing agent (hereinafter referred to as step 2).
［工程１］
工程１において使用する多価カルボン酸は、炭素系発光材料の原料であって、カルボキシル基を２つ以上有するカルボン酸であれば特に限定されない。その具体例としては、クエン酸、シュウ酸、マロン酸、コハク酸、フマル酸、イタコン酸、リンゴ酸、酒石酸等が挙げられる。これらのうち、クエン酸、コハク酸、シュウ酸が好ましく、クエン酸がより好ましい。多価カルボン酸は、１種単独でも２種以上を組み合わせて用いてもよい。
[Step 1]
The polyvalent carboxylic acid used in Step 1 is not particularly limited as long as it is a raw material for a carbon-based light emitting material and has two or more carboxyl groups. Specific examples thereof include citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, itaconic acid, malic acid, tartaric acid and the like. Of these, citric acid, succinic acid, and oxalic acid are preferable, and citric acid is more preferable. The polyvalent carboxylic acid may be used alone or in combination of two or more.
また、原料として、更にアミノ基含有有機化合物を含むことが好ましい。前記アミノ基含有有機化合物としては、アミノ酸、アミノ基含有ポリアルキレングリコール、一級脂肪族アミン等が好ましい。これらのうち、アミノ酸が特に好ましい。アミノ基含有有機化合物は、１種単独でも２種以上を組み合わせて用いてもよい。 Moreover, it is preferable that the raw material further contains an amino group-containing organic compound. As the amino group-containing organic compound, amino acids, amino group-containing polyalkylene glycols, primary aliphatic amines and the like are preferable. Of these, amino acids are particularly preferred. The amino group-containing organic compound may be used alone or in combination of two or more.
前記アミノ酸としては、グリシン、システイン、アラニン、バリン、フェニルアラニン、スレオニン、リシン、アスパラギン、トリプトファン、セリン、グルタミン酸、アスパラギン酸、オルニチン、チロキシン、シスチン、ロイシン、イソロイシン、プロリン、チロシン、アスパラギン、グルタミン、ヒスチジン、メチオニン、トレオニン等が挙げられる。アミノ基含有ポリアルキレングリコールとしては、アミノ基含有ポリエチレングリコール、アミノ基含有ポリプロピレングリコール等が挙げられる。これらのうち、グリシン、システイン、セリン等が好ましい。なお、前記アミノ酸が光学異性体を有するものである場合、前記アミノ酸はＤ体でもＬ体でもよいし、ラセミ体でもよい。 Examples of the amino acids include glycine, cysteine, alanine, valine, phenylalanine, threonine, lysine, asparagine, tryptophan, serine, glutamic acid, aspartic acid, ornithine, thyroxine, cystine, leucine, isoleucine, proline, tyrosine, asparagine, glutamine, histidine, Examples include methionine and threonine. Examples of the amino group-containing polyalkylene glycol include amino group-containing polyethylene glycol and amino group-containing polypropylene glycol. Of these, glycine, cysteine, serine and the like are preferable. When the amino acid has an optical isomer, the amino acid may be D-form, L-form, or racemate.
アミノ基含有化合物の使用量は、均一な窒素導入効率の点から、多価カルボン酸１００質量部に対して１０〜９０質量部が好ましく、２０〜８０質量部がより好ましい。 The amount of the amino group-containing compound used is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the polyvalent carboxylic acid, from the viewpoint of uniform nitrogen introduction efficiency.
原料として、更に、多価カルボン酸及びアミノ基含有有機化合物以外の有機化合物を使用してもよい。このような有機化合物としては、本発明の効果を妨げないものであれば、特に限定されない。 As the raw material, an organic compound other than the polyvalent carboxylic acid and the amino group-containing organic compound may be used. Such an organic compound is not particularly limited as long as it does not hinder the effects of the present invention.
前記酸触媒は、均一酸触媒でも不均一酸触媒でもよいが、量子収率を向上させる観点から不均一酸触媒が好ましい。均一酸触媒としては、塩酸、硫酸、硝酸、リン酸等の無機酸、スルホン酸、ｐ−トルエンスルホン酸等の有機酸が挙げられる。一方、不均一酸触媒としては、固体酸触媒が好ましく、例えば、カチオン性のイオン交換樹脂、カチオン性のイオン交換膜、Nature 438, p. 178 (2005)に記載された固体酸触媒等が挙げられる。固体酸触媒としては、市販品を使用することができ、例えば、ロームアンドハース社製イオン交換樹脂のAMBERLYST（登録商標）15、16、31、35等、AMBERLITE（登録商標）IR120B、IR124、200CT、252等、デュポン社製イオン交換膜のNAFION（登録商標）、ゼオライトやポリリン酸等の無機系固体酸触媒等が挙げられる。前記酸触媒は、１種単独でも２種以上を組み合わせて用いてもよい。 The acid catalyst may be a homogeneous acid catalyst or a heterogeneous acid catalyst, but a heterogeneous acid catalyst is preferred from the viewpoint of improving quantum yield. Examples of the homogeneous acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as sulfonic acid and p-toluenesulfonic acid. On the other hand, as the heterogeneous acid catalyst, a solid acid catalyst is preferable, and examples thereof include a cationic ion exchange resin, a cationic ion exchange membrane, and a solid acid catalyst described in Nature 438, p. 178 (2005). It is done. As the solid acid catalyst, a commercially available product can be used. , 252 and the like, NAFION (registered trademark) of an ion exchange membrane manufactured by DuPont, and inorganic solid acid catalysts such as zeolite and polyphosphoric acid. The acid catalyst may be used alone or in combination of two or more.
均一酸触媒を用いる場合、通常、均一酸触媒を原料の質量に対して０.０１〜１０質量％添加するが、０.１〜５質量％がより好ましく、０.５〜１質量％がより一層好ましい。 When a homogeneous acid catalyst is used, the homogeneous acid catalyst is usually added in an amount of 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.5 to 1% by mass with respect to the mass of the raw material. Even more preferred.
不均一酸触媒は、生成した炭素系発光材料を内包できる細孔を有する多孔質体であることが好ましい。この細孔の大きさにより生成する炭素系発光材料の粒子径又はディスク径を制御することができる。一般的には、２０ｎｍまでの細孔径を有する多孔質体の固体酸触媒により、２０ｎｍまでの粒子径（ディスク径）の炭素系発光材料を製造するのが好ましい。 The heterogeneous acid catalyst is preferably a porous body having pores that can enclose the produced carbon-based luminescent material. The particle diameter or disk diameter of the carbon-based luminescent material produced can be controlled by the size of the pores. In general, it is preferable to produce a carbon-based luminescent material having a particle diameter (disk diameter) of up to 20 nm using a porous solid acid catalyst having a pore diameter of up to 20 nm.
不均一酸触媒を用いる場合、原料の質量に対して概ね０.１〜１００質量％の添加が好ましく、１.０〜５０質量％の添加がより好ましく、５.０〜１０質量％の添加がより一層好ましい。 When using a heterogeneous acid catalyst, the addition of about 0.1 to 100% by mass is preferable with respect to the mass of the raw material, the addition of 1.0 to 50% by mass is more preferable, and the addition of 5.0 to 10% by mass is preferable. Even more preferred.
前記溶媒は、使用する原料を溶解できるものであれば特に限定されない。このような溶媒としては、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ヘキサメチルリン酸トリアミド、アセトニトリル、アセトン、アルコール類（メタノール、エタノール、１−プロパノール、２−プロパノール等）、グリコール類（エチレングリコール、トリエチレングリコール等）、セロソルブ類（エチルセロソルブ、メチルセロソルブ等）、多価アルコール類（グリセリン、ペンタエリスリトール等）、テトラヒドロフラン、トルエン、酢酸エチル、酢酸ブチル、ベンゼン、トルエン、キシレン、ペンタン、ヘキサン、ヘプタン、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、ヘキサデカン、ベンジルアルコール、オレイルアミン等が挙げられる。これらのうち、水、トルエン等が好ましい。前記溶媒は、１種単独でも２種以上を混合して用いてもよい。 The solvent is not particularly limited as long as it can dissolve the raw material to be used. Such solvents include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, acetonitrile, acetone, alcohols (methanol, ethanol, 1-propanol, 2-propanol Etc.), glycols (ethylene glycol, triethylene glycol etc.), cellosolves (ethyl cellosolve, methyl cellosolve etc.), polyhydric alcohols (glycerin, pentaerythritol etc.), tetrahydrofuran, toluene, ethyl acetate, butyl acetate, benzene, Examples include toluene, xylene, pentane, hexane, heptane, chlorobenzene, dichlorobenzene, trichlorobenzene, hexadecane, benzyl alcohol, and oleylamine. Of these, water, toluene and the like are preferable. The said solvent may be used individually by 1 type or in mixture of 2 or more types.
溶媒の使用量は、均一粒子サイズの炭素系発光材料調製の点から、原料１００質量部に対して１００〜１０,０００質量部が好ましく、４００〜２,５００質量部がより好ましい。 The amount of the solvent used is preferably 100 to 10,000 parts by mass, more preferably 400 to 2,500 parts by mass with respect to 100 parts by mass of the raw material from the viewpoint of preparing a carbon-based light emitting material having a uniform particle size.
工程１は、界面活性剤存在下で行ってもよい。前記界面活性剤としては、カチオン性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤が好ましい。 Step 1 may be performed in the presence of a surfactant. As the surfactant, a cationic surfactant, an anionic surfactant, and a nonionic surfactant are preferable.
カチオン性界面活性剤としては、セチルトリメチルアンモニウムブロマイド、セチルトリメチルアンモニウムクロライド等が挙げられる。アニオン性界面活性剤としては、ドデシル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等が挙げられる。ノニオン性界面活性剤としては、ポリエチレングリコール、ポリプロピレングリコール等が挙げられる。前記界面活性剤は、１種単独でも２種以上を組み合わせて用いてもよい。 Examples of the cationic surfactant include cetyltrimethylammonium bromide and cetyltrimethylammonium chloride. Examples of the anionic surfactant include sodium dodecyl sulfate and sodium dodecyl benzene sulfonate. Examples of nonionic surfactants include polyethylene glycol and polypropylene glycol. The surfactants may be used singly or in combination of two or more.
界面活性剤の使用量は、原料の分散性と、合成条件での臨界ミセル濃度の点から、原料１００質量部に対して１０〜２,０００質量部が好ましく、５０〜５００質量部がより好ましい。 The amount of the surfactant used is preferably 10 to 2,000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the raw material, from the viewpoint of the dispersibility of the raw material and the critical micelle concentration under the synthesis conditions. .
工程１は、原料、酸触媒、溶媒、及び必要に応じて界面活性剤を混合して、加熱するものであるが、これらの混合は、任意の順で行えばよい。例えば、原料及び必要に応じて界面活性剤をあらかじめ溶媒に加え、次いで酸触媒を加えてもよく、原料、酸触媒及び必要に応じて界面活性剤を同時に溶媒に加えてもよい。 In Step 1, a raw material, an acid catalyst, a solvent, and, if necessary, a surfactant are mixed and heated. The mixing may be performed in an arbitrary order. For example, the raw material and, if necessary, the surfactant may be added to the solvent in advance, and then the acid catalyst may be added, or the raw material, the acid catalyst, and if necessary, the surfactant may be added to the solvent at the same time.
加熱は、常圧（大気圧）下でも加圧下で行ってもよい。加圧下で行うと、常圧での沸点以上に反応温度を上げることができるため、常圧で反応させる場合と比べて、反応時間を短縮することができる。 Heating may be performed under normal pressure (atmospheric pressure) or under pressure. When the reaction is carried out under pressure, the reaction temperature can be raised above the boiling point at normal pressure, so that the reaction time can be shortened compared to the case of reacting at normal pressure.
加圧する場合は、例えば、オートクレーブを使用すればよい。オートクレーブを使用することで、常圧での沸点以上に反応温度を上げることができる。例えば、溶媒として水を使用する場合でも、オートクレーブを用いて反応させることで、２００℃程度の反応温度は容易に達成できる。 When pressurizing, for example, an autoclave may be used. By using an autoclave, the reaction temperature can be raised above the boiling point at normal pressure. For example, even when water is used as a solvent, a reaction temperature of about 200 ° C. can be easily achieved by reacting using an autoclave.
加圧は、所望の反応温度を達成できるものであれば特に限定されないが、概ね２００ｋＰａ〜２.０ＭＰａ程度が好ましく、５００ｋＰａ〜１.０ＭＰａ程度がより好ましい。 The pressurization is not particularly limited as long as the desired reaction temperature can be achieved, but is generally preferably about 200 kPa to 2.0 MPa, more preferably about 500 kPa to 1.0 MPa.
常圧で反応させる場合、反応温度は、使用する溶媒の沸点にもよるが、通常、４０〜２５０℃程度が好ましく、６０〜２００℃がより好ましく、１００〜１５０℃がより一層好ましい。加熱は、通常水浴や油浴でなされるが、マイクロ波で加熱することもできる。これによって、例えば、溶媒として水を用いる場合は、水浴や油浴で加熱する場合に比べて、短時間で生成物を得ることができる。 When the reaction is carried out at normal pressure, the reaction temperature depends on the boiling point of the solvent used, but is usually preferably about 40 to 250 ° C, more preferably 60 to 200 ° C, and still more preferably 100 to 150 ° C. Heating is usually performed in a water bath or an oil bath, but heating can also be performed with a microwave. Thus, for example, when water is used as the solvent, the product can be obtained in a shorter time than when heating in a water bath or oil bath.
常圧で反応させる場合、反応時間は、１分〜２４０時間間程度が好ましく、１０分〜４８時間程度がより好ましく、１２〜３０時間程度がより一層好ましい。加圧して反応させる場合、反応時間は、１分〜２４時間程度が好ましく、１０分〜１２時間程度がより好ましく、３０分〜３時間程度がより一層好ましい。 When the reaction is performed at normal pressure, the reaction time is preferably about 1 minute to 240 hours, more preferably about 10 minutes to 48 hours, and still more preferably about 12 to 30 hours. When the reaction is carried out under pressure, the reaction time is preferably about 1 minute to 24 hours, more preferably about 10 minutes to 12 hours, and even more preferably about 30 minutes to 3 hours.
また、固体酸触媒を用いる場合は、攪拌して反応させることが好ましく、固体触媒が砕けない範囲で、攪拌速度を上げると良い結果が得られる。攪拌速度は、１０〜５００ｒｐｍ程度が好ましく、５０〜３００ｒｐｍ程度がより好ましい。 Moreover, when using a solid acid catalyst, it is preferable to make it react by stirring, and a good result will be obtained if a stirring rate is raised in the range which a solid catalyst does not crush. The stirring speed is preferably about 10 to 500 rpm, more preferably about 50 to 300 rpm.
反応終了後、反応溶液をろ過して不純物を取り除き、そのまま工程２の還元処理を行ってもよく、反応生成物を精製した後に工程２の還元処理を行ってもよい。精製は、サイズ排除クロマトグラフィー、ペーパークロマトグラフィー、薄層クロマトグラフィー、限外ろ過等によって行うことができる。 After completion of the reaction, the reaction solution may be filtered to remove impurities, and the reduction treatment in step 2 may be performed as it is, or the reduction treatment in step 2 may be carried out after purifying the reaction product. Purification can be performed by size exclusion chromatography, paper chromatography, thin layer chromatography, ultrafiltration, and the like.
［工程２］
次いで、工程１で得られた炭素系発光材料を、還元剤を用いて還元処理する。工程２の還元処理によって、工程１で得られた炭素系発光材料の量子収率を向上させることができる。
[Step 2]
Next, the carbon-based luminescent material obtained in step 1 is reduced using a reducing agent. By the reduction treatment in step 2, the quantum yield of the carbon-based light emitting material obtained in step 1 can be improved.
還元処理は、溶媒中、工程１で得られた炭素系発光材料に還元剤を加えて、１０〜９０℃で０.１〜１００時間反応させることで行うことができる。前記溶媒としては、工程１で使用したものと同様のものが挙げられる。 The reduction treatment can be performed by adding a reducing agent to the carbon-based light-emitting material obtained in Step 1 in a solvent and reacting at 10 to 90 ° C. for 0.1 to 100 hours. Examples of the solvent include the same solvents as used in Step 1.
前記還元剤としては、水素化ホウ素ナトリウム、ヒドラジン、水素化リチウムアルミニウム、ギ酸、シュウ酸等が挙げられる。これらのうち、水素化ホウ素ナトリウム、ヒドラジン等が好ましい。 Examples of the reducing agent include sodium borohydride, hydrazine, lithium aluminum hydride, formic acid, oxalic acid and the like. Of these, sodium borohydride, hydrazine and the like are preferable.
工程２において、前記還元剤の使用量は、工程１で得られた炭素系発光材料１００質量部に対して、５０〜１,０００質量部が好ましく、１００〜５００質量部がより好ましい。また、溶媒の使用量は、工程１で得られた炭素系発光材料１００質量部に対して、５０〜２,０００質量部が好ましく、１００〜１,０００質量部がより好ましい。 In step 2, the amount of the reducing agent used is preferably 50 to 1,000 parts by mass, more preferably 100 to 500 parts by mass with respect to 100 parts by mass of the carbon-based light emitting material obtained in step 1. Moreover, 50-2,000 mass parts is preferable with respect to 100 mass parts of carbon-type luminescent materials obtained at the process 1, and the usage-amount of a solvent has more preferable 100-1,000 mass parts.
本発明の方法で製造された炭素系発光材料は、化学的安定性、発光量子収率、発光特性制御等の点から、グラフェン構造を含むものであることが好ましい。また、前記炭素系発光材料は、波長２００〜３８０ｎｍの励起光によって、波長３８０〜４８０ｎｍの光を発するものであることが好ましい。 The carbon-based light-emitting material produced by the method of the present invention preferably contains a graphene structure from the viewpoints of chemical stability, light emission quantum yield, light emission characteristic control, and the like. The carbon-based light emitting material preferably emits light having a wavelength of 380 to 480 nm by excitation light having a wavelength of 200 to 380 nm.
以下、実施例及び比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されない。なお、使用した装置は以下のとおりである。
（１）サイズ排除クロマトグラフィー：ガラス製オープンカラム（φ３５ｍｍ×４００ｍｍ）、充填剤：東ソー(株)製ＴＯＹＯＰＥＡＲＬ（登録商標）ＨＷ−４０Ｆ（２５０ｍＬ）、展開溶媒：水
（２）蛍光スペクトル：日本分光(株)製ＦＰ−６５００
（３）量子収率の測定：(株)島津製作所製ＵＶ−３６００及び日本分光(株)製ＦＰ−６５００
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the apparatus used is as follows.
(1) Size exclusion chromatography: glass open column (φ35 mm × 400 mm), packing material: TOYOPEARL (registered trademark) HW-40F (250 mL) manufactured by Tosoh Corporation, developing solvent: water (2) fluorescence spectrum: JASCO FP-6500, manufactured by
(3) Measurement of quantum yield: Shimadzu Corporation UV-3600 and JASCO Corporation FP-6500
［比較例１］
５０ｍＬサンプルビンに、クエン酸一水和物０.７４ｇ（３.５ｍｍｏｌ）及びグリシン０.２６ｇ（３.５ｍｍｏｌ）を脱イオン水２５ｍＬに溶解した溶液を入れた。前記溶液に、攪拌子及びＡＭＢＥＲＬＹＳＴ １５ ０.０５ｇを加えた。これをステンレス製オートクレーブ内に装着したテフロン（登録商標）製インナー内に装着し、４５分かけて２００℃まで昇温して２時間攪拌しながら反応させた。
その後、室温まで放冷し、ＡＭＢＥＲＬＹＳＴ １５を０.２μｍフィルターでろ別した。ろ液から水を留去し、得られた固形物にメタノール５０ｍＬを加え、不溶物をろ別し、ろ液から溶媒を留去し、黒色粘凋体である反応粗製物を得た。
前記反応粗製物に脱イオン水５ｍＬを加え、サイズ排除クロマトグラフィーによって分子量で分画し、分子量が１０2〜１０4である炭素系発光材料１含有分散液を得た。
[Comparative Example 1]
A 50 mL sample bottle was charged with a solution of 0.74 g (3.5 mmol) citric acid monohydrate and 0.26 g (3.5 mmol) glycine in 25 mL deionized water. A stir bar and 0.05 g of AMBERLYST 15 were added to the solution. This was mounted in a Teflon (registered trademark) inner mounted in a stainless steel autoclave, heated to 200 ° C. over 45 minutes, and allowed to react with stirring for 2 hours.
Thereafter, the mixture was allowed to cool to room temperature, and AMBERLYST 15 was filtered off with a 0.2 μm filter. Water was distilled off from the filtrate, 50 mL of methanol was added to the resulting solid, insoluble matter was filtered off, and the solvent was distilled off from the filtrate to obtain a reaction crude product that was a black viscous body.
5 mL of deionized water was added to the reaction crude product and fractionated by molecular weight by size exclusion chromatography to obtain a carbon-based luminescent material 1-containing dispersion having a molecular weight of 10 2 to 10 4 .
［実施例１］
容器に前記炭素系発光材料１含有分散液を加え、更に脱イオン水を加えて濃度が１ｍｇ／ｍＬになるように調整した。そこに抱水ヒドラジン３ｍＬを加え、容器を密閉して８０℃で２４時間反応させ、その後室温まで冷却し、炭素系発光材料２含有分散液を得た。
[Example 1]
The carbon-based luminescent material 1-containing dispersion was added to the container, and deionized water was further added to adjust the concentration to 1 mg / mL. Thereto was added 3 mL of hydrazine hydrate, and the container was sealed and reacted at 80 ° C. for 24 hours, and then cooled to room temperature to obtain a carbon-based luminescent material 2-containing dispersion.
［実施例２］
前記炭素系発光材料１含有分散液（１ｍｇ／ｍＬ）２ｍＬに、抱水ヒドラジンのかわりに水素化ホウ素ナトリウム３ｍｇ（終濃度２５ｍＭ）を加えた以外は、実施例１と同じ方法で炭素系発光材料３含有分散液を得た。
[Example 2]
The carbon-based luminescent material was prepared in the same manner as in Example 1, except that 3 mg of sodium borohydride (final concentration: 25 mM) was added to 2 mL of the carbon-based luminescent material 1-containing dispersion (1 mg / mL) instead of hydrazine hydrate. A 3 containing dispersion was obtained.
［量子収率の測定］
比較例１、実施例１〜２で得られた炭素系発光材料について、蛍光スペクトル及び量子収率の測定を行った。結果を表１に示す。
[Measurement of quantum yield]
For the carbon-based luminescent materials obtained in Comparative Example 1 and Examples 1-2, the fluorescence spectrum and quantum yield were measured. The results are shown in Table 1.
表１に示したように、工程１の方法で得られた炭素系発光材料を還元剤で処理することによって、量子収率を向上させることができた。 As shown in Table 1, the quantum yield could be improved by treating the carbon-based luminescent material obtained by the method of Step 1 with a reducing agent.
Claims (10)
前記工程で得られた炭素系発光材料を、還元剤を用いて還元処理する工程
を含む炭素系発光材料の製造方法。 A step of mixing a raw material containing a polyvalent carboxylic acid, an acid catalyst and a solvent and heating to produce a carbon-based luminescent material, and a reduction treatment of the carbon-based luminescent material obtained in the step using a reducing agent The manufacturing method of the carbon-type luminescent material including a process.
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