JP5610460B2 - Nanoparticle dispersible in water and method for producing nanoparticle dispersion - Google Patents
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本発明は、水分散可能なナノ粒子、その水性分散液、及びその製造方法に関する。 The present invention relates to water-dispersible nanoparticles, an aqueous dispersion thereof, and a production method thereof.
ナノサイズの炭素材料、金属、金属酸化物、金属硫化物などは、その微細な内部構造に基づく、サイズ特異的な蛍光などの特殊な機能の発現が知られている。また、光の波長より小さな粒径を持つ粒子を分散したものは透明になる。このような特徴を有するナノ粒子の水分散液は、インク、化粧品、医療分野をはじめ幅広い分野での応用が期待されている。 Nano-sized carbon materials, metals, metal oxides, metal sulfides, and the like are known to exhibit special functions such as size-specific fluorescence based on their fine internal structure. In addition, a dispersion in which particles having a particle size smaller than the wavelength of light are dispersed becomes transparent. An aqueous dispersion of nanoparticles having such characteristics is expected to be applied in a wide range of fields including ink, cosmetics, and medical fields.
ナノ粒子の水分散液の調製法は、安定剤、分散剤共存下で原料物質溶液から化学反応によりナノ粒子を発生させる方法が良く知られている。また、事前に調製したナノ粒子を何らかの手法で水分散させる方法もある。
特に後者の手法でナノ粒子の水分散液を作成ためには、通常は高度に凝集して二次粒子となっているナノ粒子を、ビーズミル、超音波ホモジナイザー、アルティマイザーなどの機器を用いて解砕し、その後、ナノ粒子表面を改質して水への親和性を向上させるという二つの技術要素が必要である。
As a method for preparing an aqueous dispersion of nanoparticles, a method of generating nanoparticles by a chemical reaction from a raw material solution in the presence of a stabilizer and a dispersant is well known. There is also a method in which nanoparticles prepared in advance are dispersed in water by some technique.
In particular, in order to create an aqueous dispersion of nanoparticles using the latter method, nanoparticles that are usually highly agglomerated and formed into secondary particles are dissolved using a device such as a bead mill, an ultrasonic homogenizer, or an optimizer. Two technical elements are needed: crushing and then modifying the nanoparticle surface to improve its affinity for water.
このナノ粒子表面の改質については、粒子の化学組成によっていくつかの手法がある。
たとえば、カーボンナノチューブやカーボンナノホーンをはじめとする元来疎水性である炭素材料ナノ粒子については、化学反応により、その表面に親水性官能基であるカルボキシル基などを直接発現させる方法がある(特許文献１)。また、界面活性剤を水分散コーティング剤としてコーティングすることによって水分散させることも可能である(特許文献２)。
一方、シリカ、酸化チタンなどの金属を組成に含む無機ナノ粒子の場合、金属と結合可能な官能基と親水性の両方を有する分散剤を用いる方法や(特許文献３)、はじめにナノ粒子表面を疎水処理した後に、高分子の非イオン性界面活性剤でコーティングする方法がある(特許文献４)。
There are several methods for modifying the nanoparticle surface depending on the chemical composition of the particles.
For example, for carbon material nanoparticles that are inherently hydrophobic, such as carbon nanotubes and carbon nanohorns, there is a method in which a carboxyl group, which is a hydrophilic functional group, is directly expressed on the surface by a chemical reaction (Patent Literature). 1). Moreover, it is also possible to carry out water dispersion by coating surfactant as a water dispersion coating agent (patent document 2).
On the other hand, in the case of inorganic nanoparticles containing a metal such as silica or titanium oxide, a method using a dispersant having both a functional group capable of binding to a metal and a hydrophilic property (Patent Document 3), There is a method of coating with a polymeric nonionic surfactant after hydrophobic treatment (Patent Document 4).
しかしながら、高分子の非イオン性界面活性剤を、水分散コーティング剤として用いる場合、前処理としてナノ粒子表面に低分子を用いて有機溶媒中で疎水処理を行なうなど、多数かつ煩雑な工程を必要とする。
一方、低分子量の水分散コーティング剤を用いて作成したナノ粒子分散液は、乾燥すると、ナノ粒子が凝集、溶着を起こす。凝集、溶着したナノ粒子は水への再分散が困難であるか、あるいは当初の分散状態と異なった状態になることがある。
ナノ粒子の輸送、保管を考えると、乾燥固体の方が重量、容量の点で有利であるが、以上の背景から、水分散コーティング剤を用いて作成したナノ粒子は乾燥させず、分散液の状態で取り扱う必要があった。
また、現存の水分散コーティング剤は、粒子表面に対して個別に設計され、さらにそのコーティング法もコアとなる粒子ごとに異なり、汎用性が高くないという問題もある。
However, when polymer nonionic surfactants are used as water-dispersed coating agents, a number of complicated steps are required, such as hydrophobic treatment in an organic solvent using low molecules on the nanoparticle surface as a pretreatment. And
On the other hand, when a nanoparticle dispersion prepared using a low molecular weight water-dispersed coating agent is dried, the nanoparticles aggregate and weld. Agglomerated and welded nanoparticles may be difficult to redisperse in water or may be in a different state from the original dispersed state.
Considering the transportation and storage of nanoparticles, dry solids are more advantageous in terms of weight and volume, but from the above background, nanoparticles made using water-dispersed coating agents are not dried and It was necessary to handle in a state.
In addition, existing water-dispersed coating agents are individually designed with respect to the particle surface, and the coating method differs depending on the core particles, and there is a problem that versatility is not high.
本発明は、このような事情を鑑みてなされたものであって、水分散液から乾燥しても、凝集、溶着を起こさず、水に再分散が可能で、水分散性の良好な微粒子を得ることを目的とするものである。また、本発明の別の目的は、種々のコア粒子をもつ水分散性ナノ粒子を、安価、かつ汎用性の高い低分子コーティング剤を用いて、簡便に製造することにある。 The present invention has been made in view of such circumstances, and fine particles having good water dispersibility can be obtained by redispersing in water without causing aggregation and welding even when dried from an aqueous dispersion. It is intended to obtain. Another object of the present invention is to easily produce water-dispersible nanoparticles having various core particles using a low-molecular coating agent that is inexpensive and highly versatile.
ナノ粒子の分散液を乾燥するとナノ粒子同士の凝集、溶着を起こすのは、この低分子量の水分散コーティング剤が、室温付近で液晶もしくは溶解状態であるものが多く、例えば、ドデシル硫酸ナトリウムは室温では水に溶解状態であり、そのために、乾燥の際に容易に分散剤同士の融合が起きるためであると考えられる。
水分散コーティング剤として用いる低分子両親媒性化合物は、親水基Ａ、疎水基Ｂの両方を分子内に持ち、一般式Ａ−Ｂで表される化合物であるが、本発明者等がこの問題を解決すべく検討した結果、乾燥による凝集、溶着を抑制するためには、該両親媒性化合物として、コーティング状態で溶解せず、ゲル−液晶相転移温度が室温より高く、水の沸点より低いものを用い、凝集したナノ粒子に、該両親媒性化合物及び水を加えた後、その相転移温度以上に加熱しながら解砕・混合することにより、ナノ粒子表面に安定な結晶性の両親媒性化合物からなる皮膜を形成することができることを見いだした。
When the nanoparticle dispersion is dried, the nanoparticles are agglomerated and welded with each other. This low molecular weight water-dispersed coating agent is often in a liquid crystal or dissolved state near room temperature.For example, sodium dodecyl sulfate is used at room temperature. In this case, it is considered that it is in a dissolved state in water, and therefore, the fusion of the dispersants easily occurs during drying.
The low molecular weight amphiphilic compound used as the water-dispersible coating agent is a compound having both a hydrophilic group A and a hydrophobic group B in the molecule and represented by the general formula AB. As a result of studying to solve the problem, in order to suppress aggregation and welding due to drying, the amphiphilic compound does not dissolve in the coating state, and the gel-liquid crystal phase transition temperature is higher than room temperature and lower than the boiling point of water. After adding the amphiphilic compound and water to the agglomerated nanoparticles, and crushing and mixing while heating above the phase transition temperature, the crystalline amphiphile stable on the nanoparticle surface It has been found that a film made of a functional compound can be formed.
さらに、本発明者らが検討したところ、このような特徴を持つ水分散コーティング剤の分子構造として、Ａの親水部は、単糖や複糖もしくは、オリゴペプチド、ＰＥＯなどで、好ましくは単糖もしくはアミノ酸３個以下のペプチドで、より好ましくは単糖ではグルコース、アミノ酸はグリシンであり、また、Ｂの疎水部については飽和、不飽和のアルキルまたは芳香族やその他の元素を含んでも良いが、好ましくは炭素鎖が１０から２４の飽和もしくは不飽和の脂肪族であることが判明した。 Furthermore, as a molecular structure of the water-dispersed coating agent having such characteristics, the present inventors have studied that the hydrophilic part of A is a monosaccharide, a disaccharide, an oligopeptide, PEO or the like, preferably a monosaccharide. Alternatively, it is a peptide of 3 amino acids or less, more preferably glucose for monosaccharides, and glycine for amino acids, and the hydrophobic part of B may contain saturated or unsaturated alkyl or aromatic or other elements, Preferably, the carbon chain has been found to be 10 to 24 saturated or unsaturated aliphatic.
本発明はこれらの知見に基づいて完成に至ったものであり、本発明によれば、以下の発明が提供される。
［１］ナノ粒子の表面が、ゲル−液晶相転移温度が室温より高く、かつ水の沸点より低い両親媒性化合物からなる結晶性物質で被覆されてなる易分散性ナノ粒子であって、前記両親媒性化合物が、
下記一般式（１）
Ｇ−ＮＨＣＯ−Ｒ １ （１）
（式中、Ｇは糖のアノマー炭素原子に結合するヘミアセタール水酸基を除いた糖残基を表し、Ｒ １ は炭素数が１０〜２４の不飽和炭化水素基を表す。）
で表わされるＮ−グリコシド型糖脂質、
下記一般式（２）
Ｒ ２ ＣＯ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＯＨ (２)
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質、又は
下記一般式（３）
Ｈ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＮＨＲ ２ （３）
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質、
のいずれかであることを特徴とする易分散性ナノ粒子。
［２］上記［１］の易分散性ナノ粒子が、水中に分散されてなるナノ粒子水分散液。
［３］ナノ粒子を、その表面を被覆することにより水中に分散させるための分散剤であって、
ゲル−液晶相転移温度が室温より高く、かつ水の沸点より低い両親媒性化合物からなる結晶性物質を有効成分とし、前記両親媒性化合物が、
下記一般式（１）
Ｇ−ＮＨＣＯ−Ｒ １ （１）
（式中、Ｇは糖のアノマー炭素原子に結合するヘミアセタール水酸基を除いた糖残基を表し、Ｒ １ は炭素数が１０〜２４の不飽和炭化水素基を表す。）
で表わされるＮ−グリコシド型糖脂質、
下記一般式（２）
Ｒ ２ ＣＯ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＯＨ (２)
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表されるペプチド脂質、又は
下記一般式（３）
Ｈ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＮＨＲ ２ （３）
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質、
のいずれかであることを特徴とするナノ粒子用分散剤。
［４］ナノ粒子に、上記［３］のナノ粒子用分散剤及び水を加えた後、前記相転移温度以上に加熱しながら攪拌混合することを特徴とするナノ粒子の分散液の製造方法。
The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] The easily dispersible nanoparticles in which the surface of the nanoparticles is coated with a crystalline substance composed of an amphiphilic compound having a gel-liquid crystal phase transition temperature higher than room temperature and lower than the boiling point of water , Amphiphilic compounds
The following general formula (1)
G-NHCO-R 1 (1)
(In the formula, G represents a sugar residue excluding the hemiacetal hydroxyl group bonded to the anomeric carbon atom of the sugar, and R 1 represents an unsaturated hydrocarbon group having 10 to 24 carbon atoms.)
N-glycoside type glycolipid represented by
The following general formula (2)
R 2 CO (NH-CHR 3 -CO) m OH (2)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by:
The following general formula (3)
H (NH—CHR 3 —CO) m NHR 2 (3)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by
An easily dispersible nanoparticle characterized by being one of the following .
[ 2 ] A nanoparticle aqueous dispersion in which the easily dispersible nanoparticles of [1] are dispersed in water.
[ 3 ] A dispersant for dispersing nanoparticles in water by coating the surface thereof ,
A crystalline substance composed of an amphiphilic compound having a gel-liquid crystal phase transition temperature higher than room temperature and lower than the boiling point of water is an active ingredient, and the amphiphilic compound is:
The following general formula (1)
G-NHCO-R 1 (1)
(In the formula, G represents a sugar residue excluding the hemiacetal hydroxyl group bonded to the anomeric carbon atom of the sugar, and R 1 represents an unsaturated hydrocarbon group having 10 to 24 carbon atoms.)
N-glycoside type glycolipid represented by
The following general formula (2)
R 2 CO (NH-CHR 3 -CO) m OH (2)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by:
The following general formula (3)
H (NH—CHR 3 —CO) m NHR 2 (3)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by
Dispersants for nanoparticles characterized by either der Rukoto of.
[ 4 ] A method for producing a dispersion of nanoparticles, comprising adding the nanoparticle dispersant for water of [ 3 ] and water to the nanoparticles, followed by stirring and mixing while heating at or above the phase transition temperature.
本発明の易分散性ナノ粒子は、コアとして炭素材料としてカーボンナノホーン、金属を組成に含む材料として酸化亜鉛(ＺｎＯ)、マグネタイト(Ｆｅ３Ｏ４)、二酸化チタンと広範で汎用性が高い。また、カーボンナノホーンについては２０ｇ／Ｌと極めて高濃度でカーボンナノホーンを分散することができる。動的光散乱測定では、いずれのナノ粒子の場合も、本発明の操作前と操作後では粒径が減少しており、二次粒子の解砕と、コーティングによる水分散性の向上が一つの工程で、かつ短時間で達成される。これまでのコーティングよるナノ粒子水分散液の作成は途中に有機溶媒の使用を含む多段階の操作が必要なものも多かったのに対して、本発明によれば、１工程で、かつ使用する媒体が水のみであるためコスト的にも有利である。また、本発明により作成された易分散性ナノ粒子は、乾燥して、再分散できるため、保存、輸送時には省スペース、軽量化が可能となり、大きなアドバンテージが期待できる。 The easily dispersible nanoparticles of the present invention have a wide range and high versatility such as carbon nanohorn as a carbon material as a core, zinc oxide (ZnO), magnetite (Fe 3 O 4 ), and titanium dioxide as materials containing a metal in the composition. Further, carbon nanohorns can be dispersed at an extremely high concentration of 20 g / L. In the dynamic light scattering measurement, in any nanoparticle, the particle size is reduced before and after the operation of the present invention, and the secondary particle crushing and the improvement of water dispersibility by coating are one of the reasons. It is achieved in a short time in the process. The preparation of aqueous nanoparticle dispersions by conventional coatings often requires multi-step operations including the use of organic solvents, but according to the present invention, it is used in one step. Since the medium is only water, it is advantageous in terms of cost. In addition, since the easily dispersible nanoparticles prepared according to the present invention can be dried and redispersed, it is possible to save space and weight during storage and transportation, and a great advantage can be expected.
図１は、本発明を説明するための概念図である。
図に示すように、本発明のナノ粒子は、結晶性両親媒性化合物で被覆されて、水分散可能とされていることを特徴とする。
本発明において、水分散コーティング剤として用いる両親媒性化合物は、親水基Ａと疎水基Ｂの両方を分子内に持ち、一般式Ａ−Ｂで表される化合物である。分散液から乾燥したナノ粒子が凝集、溶着を起こすのは、この化合物が、媒体中、室温で液晶もしくは溶解状態だからである。本発明においては、乾燥による凝集、溶着を抑制するため、該両親媒性化合物として、コーティング状態で溶解せず、ゲル−液晶相転移温度が室温より高く、かつ水の沸点より低いものを用いる。
FIG. 1 is a conceptual diagram for explaining the present invention.
As shown in the figure, the nanoparticles of the present invention are characterized in that they are coated with a crystalline amphiphilic compound and are water dispersible.
In the present invention, the amphiphilic compound used as a water-dispersed coating agent is a compound having both a hydrophilic group A and a hydrophobic group B in the molecule and represented by the general formula AB. The nanoparticles dried from the dispersion cause aggregation and welding because this compound is liquid crystal or dissolved in the medium at room temperature. In the present invention, in order to suppress aggregation and welding due to drying, an amphiphilic compound that does not dissolve in a coating state and has a gel-liquid crystal phase transition temperature higher than room temperature and lower than the boiling point of water is used.
このような該両親媒性化合物の親水基Ａは、単糖や複糖もしくは、オリゴペプチド、ＰＥＯなどで、好ましくは、単糖もしくはアミノ酸３個以下のペプチドで、より好ましくは、単糖ではグルコース、アミノ酸はグリシンである。
また、疎水基Ｂは、飽和、不飽和のアルキルまたは芳香族やその他の元素を含んでも良いが、好ましくは炭素鎖が１０から２４の飽和もしくは不飽和の脂肪族である。また直鎖型だけでなく分岐していても良いが、一般的にはアルキル鎖は炭素数が多く、かつ直鎖型で相転移点が高くなる傾向がある。
The hydrophilic group A of the amphiphilic compound is a monosaccharide, a disaccharide, an oligopeptide, PEO, or the like, preferably a monosaccharide or a peptide having 3 or less amino acids, and more preferably a monosaccharide is glucose. The amino acid is glycine.
The hydrophobic group B may contain saturated or unsaturated alkyl or aromatic or other elements, but is preferably saturated or unsaturated aliphatic having 10 to 24 carbon chains. In addition to the straight chain type, it may be branched, but in general, the alkyl chain has a large number of carbon atoms and tends to have a high phase transition point in the straight chain type.
また、分子構造内にアミドなど分子間相互作用を引き起こす官能基を有し、これが隣接する両親媒性化合物と水素結合などを介して安定な結晶性の分子膜を形成するものがよく、具体的には、特開２００８−３０１８５号公報、特開２００８−３１１５２号公報等において、有機ナノチューブの原料として用いられるところの、下記一般式（１）
Ｇ−ＮＨＣＯ−Ｒ１ （１）
（式中、Ｇは糖のアノマー炭素原子に結合するヘミアセタール水酸基を除いた糖残基を表し、Ｒ１は炭素数が１０〜２４の不飽和炭化水素基を表す。）
で表わされるＮ−グリコシド型糖脂質、又は下記一般式（２）
Ｒ２ＣＯ（ＮＨ−ＣＨＲ３−ＣＯ）ｍＯＨ (２)
（式中、Ｒ２は炭素数１０〜２４の炭化水素基、Ｒ３はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質、又は下記一般式（３）
Ｈ（ＮＨ−ＣＨＲ３−ＣＯ）ｍＮＨＲ２ （３）
（式中、Ｒ２は炭素数１０〜２４の炭化水素基、Ｒ３はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質があげられ、好ましく用いられる。
In addition, a functional group that causes an intermolecular interaction such as an amide in the molecular structure, and this forms a stable crystalline molecular film with an adjacent amphiphilic compound through a hydrogen bond, etc. The following general formula (1), which is used as a raw material for organic nanotubes in Japanese Patent Application Laid-Open Nos. 2008-30185 and 2008-31152, etc.
G-NHCO-R 1 (1)
(In the formula, G represents a sugar residue excluding the hemiacetal hydroxyl group bonded to the anomeric carbon atom of the sugar, and R 1 represents an unsaturated hydrocarbon group having 10 to 24 carbon atoms.)
N-glycoside type glycolipid represented by the following general formula (2)
R 2 CO (NH-CHR 3 -CO) m OH (2)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
Or a peptide lipid represented by the following general formula (3)
H (NH—CHR 3 —CO) m NHR 2 (3)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
And are preferably used.
本発明者らは、上記の特許公開公報に記載されているように、上記のＮ−グリコシド型糖脂質又はペプチド脂質を、有機溶媒中で自己集合させることによって、無水有機ナノチューブを簡便かつ大量に製造できることを見いだしたが、その後の検討の結果、これらのＮ−グリコシド型糖脂質又はペプチド脂質は、両親媒性化合物であって、かつ、ゲル−液晶相転移温度が室温より高く、かつ水の沸点より低いものであるため、ナノ微粒子の水分散剤として有用であることが判明したものである。 As described in the above-mentioned patent publications, the present inventors self-assemble the N-glycoside type glycolipid or peptide lipid in an organic solvent, thereby easily and in large quantities of anhydrous organic nanotubes. As a result of subsequent studies, these N-glycoside type glycolipids or peptide lipids are amphiphilic compounds and have a gel-liquid crystal phase transition temperature higher than room temperature and water. Since it is lower than the boiling point, it has been found to be useful as a water dispersion agent for nanoparticles.
本発明において用いられる両親媒性化合物は、上述の特徴を有する２種類以上を併用しても良く、両親媒性化合物に混合して分子膜を形成するその他の化合物が共存しても良い。 Two or more types of the amphiphilic compounds used in the present invention may be used in combination, or other compounds that form a molecular film by mixing with the amphiphilic compounds may coexist.
一方、本発明において、コアとなる粒子は、水の沸点や、コーティングする両親媒性化合物の相転移温度の条件で溶融、分解しないものであれば良い。好ましくはカーボンナノホーンなどの炭素を主たる組成に持つナノ粒子、またはマグネタイト、酸化亜鉛、酸化チタン、酸化カルシウム、シリカなどの金属酸化物、硫化カドミウムなど金属カルコゲン化物、硫酸バリウムなどの塩などである。 On the other hand, in the present invention, the core particles may be any particles that do not melt or decompose under the conditions of the boiling point of water and the phase transition temperature of the amphiphilic compound to be coated. Preferred are nanoparticles having a main composition of carbon such as carbon nanohorn, metal oxides such as magnetite, zinc oxide, titanium oxide, calcium oxide and silica, metal chalcogenides such as cadmium sulfide, and salts such as barium sulfate.
コアとなるナノ粒子は凝集して二次粒子を作っていることが多いが、本発明のナノ粒子の製造方法は、凝集している二次粒子の解砕と、両親媒性化合物の相点移転以上での加熱を同時に行なうことを特徴とするものである。
すなわち、加熱により、その相転移温度より高温となり、液晶状態となった両親媒性化合物が、解砕されたナノ粒子をコアとしてコーティングされ、その後、冷却により、両親媒性化合物が、その親水基を外表面側に配向した安定な結晶性の皮膜を形成し、水分散性ナノ粒子ができる。
In many cases, core nanoparticles are aggregated to form secondary particles. However, the method for producing nanoparticles of the present invention is based on the crushing of aggregated secondary particles and the phase of amphiphilic compounds. It is characterized in that heating beyond the transfer is performed at the same time.
That is, by heating, the amphiphilic compound that is higher in temperature than its phase transition temperature and in a liquid crystal state is coated with the crushed nanoparticles as a core, and then cooled to convert the amphiphilic compound to its hydrophilic group. Is formed on the outer surface side to form a stable crystalline film, thereby forming water-dispersible nanoparticles.
この二つのプロセスを同時に行なう手段としてはアルティマイザー、超音波ホモジナイザー、ボールミルなどが挙げられるが、より好ましくはアルティマイザー、超音波ホモジナイザーである。
アルティマイザーの場合、チャンバー内で発生する熱により処理液温度が水分散コーティング剤の相転移温度より高温となり、液晶状態となった水分散コーティング剤が解砕されたナノ粒子をコアとしてコーティングする。
また、超音波ホモジナイザーの場合、超音波照射による発熱が十分でないときには処理液温が水分散コーティング剤の相転移点より高くなるように外部からの加熱し、液晶状態となった水分散コーティング剤が超音波により解砕されたナノ粒子をコアとしてコーティングする。
本発明において、コアとなる粒子と両親媒性化合物の重量比は１：０．１〜１：１０の間である。
Examples of means for simultaneously performing these two processes include an optimizer, an ultrasonic homogenizer, and a ball mill. More preferred are an optimizer and an ultrasonic homogenizer.
In the case of the optimizer, the heat generated in the chamber causes the treatment liquid temperature to be higher than the phase transition temperature of the water-dispersed coating agent, and the nanoparticles dispersed in the liquid-dispersed water-dispersed coating agent are coated as a core.
In addition, in the case of an ultrasonic homogenizer, when heat generation due to ultrasonic irradiation is not sufficient, the water dispersion coating agent in a liquid crystal state is heated from the outside so that the treatment liquid temperature becomes higher than the phase transition point of the water dispersion coating agent. The nanoparticles crushed by ultrasonic waves are coated as a core.
In the present invention, the weight ratio between the core particles and the amphiphilic compound is between 1: 0.1 and 1:10.
以下、本発明を実施例に基づいて説明するが、本発明はこの実施例に限定されるものではない。
〈使用した分散剤〉
本実施例では、両親媒性化合物として、１−アミノグルコピラノシドとオレイン酸がアミド結合により連結した次式で表される化合物（両親媒性化合物１とする。）
なお、両親媒性化合物１及び両親媒性化合物２は、水中でのゲル−液晶相転移温度が、それぞれ６８℃及び５４℃で、いずれも室温で安定な結晶状態である。
を用いた。
また、比較例として、市販のTween80（非イオン性界面活性剤）及びドデシル硫酸ナトリウム（ＳＤＳ、アニオン性界面活性剤）を用いた。
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to this Example.
<Dispersant used>
In this example, as an amphiphilic compound, a compound represented by the following formula in which 1-aminoglucopyranoside and oleic acid are linked by an amide bond (referred to as amphiphilic compound 1).
In addition, the amphiphilic compound 1 and the amphiphilic compound 2 have a gel-liquid crystal phase transition temperature in water of 68 ° C. and 54 ° C., respectively, and both are stable crystalline states at room temperature.
Was used.
As a comparative example, commercially available Tween 80 (nonionic surfactant) and sodium dodecyl sulfate (SDS, anionic surfactant) were used.
（実施例１：アルティマイザーを用いた、カーボンナノホーンをコアとするナノ粒子の作成）
カーボンナノホーン（ダリア状に集合した集合体を一次粒子として、その径が約１００ｎｍ）を１０００ｍｇ、上記両親媒性化合物１を１０００ｍｇ、はかり取り、蒸留水２Ｌを加えた。この混合物をホモジナイザーで３０分撹拌した後、アルティマイザー（スギノマシンHJP25005）に投入し、圧力２４５ＭＰａで１００パスし、両親媒性化合物でコーティングされたナノ粒子の水分散液を得た。
動的光散乱ではパス数の増大ともに粒径の減少が観察され、１００パスで一次粒径の粒子サイズとなった（８０〜９０ｎｍ）。このナノ粒子水分散液はその後１週間以上沈殿を生じず、安定な分散状態を保った。
さらにこのナノ粒子を凍結乾燥後、水に再分散したところ、若干粒径が上がるもの（９０〜１２０ｎｍ）、ナノ粒子の良好な分散液が得られた。
(Example 1: Creation of nanoparticles using carbon nanohorn as a core using an optimizer)
1000 mg of carbon nanohorn (aggregate aggregated in dahlia as primary particles, the diameter is about 100 nm), 1000 mg of the amphiphilic compound 1 were weighed, and 2 L of distilled water was added. The mixture was stirred with a homogenizer for 30 minutes, and then charged into an optimizer (Sugino Machine HJP25005) and passed for 100 passes at a pressure of 245 MPa to obtain an aqueous dispersion of nanoparticles coated with an amphiphilic compound.
In dynamic light scattering, a decrease in particle size was observed with an increase in the number of passes, and the particle size of the primary particle size was reached in 100 passes (80 to 90 nm). This nanoparticle aqueous dispersion did not precipitate for more than one week thereafter, and maintained a stable dispersion state.
Furthermore, when these nanoparticles were lyophilized and then redispersed in water, a slightly increased particle size (90 to 120 nm) and a good dispersion of nanoparticles were obtained.
（比較例１：ＳＤＳによってコーティングされたカーボンナノホーンをコアとするナノ粒子の作成）
カーボンナノホーンを３７５ｍｇ、両親媒性化合物としてＳＤＳを３７５ｍｇ、はかり取り、蒸留水７５０ｍＬを加えた。この混合物をホモジナイザーで３０分撹拌した後、アルティマイザーに投入し、圧力２４５ＭＰａで１００パスし、ＳＤＳでコーティングされたナノ粒子の水分散液を得た。
動的光散乱では１パス以降、数の増大による粒径の変化は観察されなかった。１００パスで一次粒径の粒子サイズ（９０〜１００ｎｍ）となった。このナノ粒子水分散液はその後１週間以上沈殿を生じず、安定な分散状態を保った。
さらにこのナノ粒子を乾燥後、水に再分散したところ、濃縮による溶着は見られず、若干粒径が上がるもの（１２０〜１３０ｎｍ）、ナノ粒子の良好な分散液が得られた。
(Comparative Example 1: Production of nanoparticles having carbon nanohorn coated with SDS as a core)
375 mg of carbon nanohorn and 375 mg of SDS as an amphiphilic compound were weighed out and 750 mL of distilled water was added. The mixture was stirred with a homogenizer for 30 minutes, and then charged into an optimizer and passed through 100 passes at a pressure of 245 MPa to obtain an aqueous dispersion of nanoparticles coated with SDS.
In dynamic light scattering, no change in particle size due to an increase in number was observed after one pass. The particle size (90 to 100 nm) of the primary particle size was obtained after 100 passes. This nanoparticle aqueous dispersion did not precipitate for more than one week thereafter, and maintained a stable dispersion state.
Further, when the nanoparticles were dried and redispersed in water, no welding due to concentration was observed, and a slightly increased particle size (120 to 130 nm), a good dispersion of nanoparticles was obtained.
（実施例２：超音波ホモジナイザーを用いた、カーボンナノホーンをコアとするナノ粒子の作成）
カーボンナノホーンを６．３ｍｇ、上記両親媒性化合物１を６．３ｍｇ、量り取り、蒸留水５０ｍＬを加えた。この混合物をホモジナイザーで３０分撹拌した後、液温が８０℃を保つように加熱しながらプローブ式超音波発生装置による超音波照射をおこない(１２０Ｗ)、両親媒性化合物でコーティングされたナノ粒子の水分散液を得た。
動的光散乱では６０分照射後に、一次粒径の粒子サイズ（９０〜１１０ｎｍ）となり、その後の粒径変化は認められなかった。このナノ粒子水分散液はその後１週間以上沈殿を生じず、安定な分散状態を保った。
さらにこのナノ粒子を凍結乾燥後、水に再分散したところ、若干粒径が上がるもの（１３０〜１５０ｎｍ）、ナノ粒子の良好な分散液が得られた。
(Example 2: Preparation of nanoparticles having carbon nanohorn as a core using an ultrasonic homogenizer)
6.3 mg of carbon nanohorn and 6.3 mg of the amphiphilic compound 1 were weighed out and 50 mL of distilled water was added. The mixture was stirred for 30 minutes with a homogenizer, and then irradiated with ultrasonic waves using a probe-type ultrasonic generator (120 W) while heating so that the liquid temperature was kept at 80 ° C., and the nanoparticles coated with the amphiphilic compound An aqueous dispersion was obtained.
In dynamic light scattering, the particle size of the primary particle size (90 to 110 nm) was obtained after 60 minutes of irradiation, and no subsequent change in particle size was observed. This nanoparticle aqueous dispersion did not precipitate for more than one week thereafter, and maintained a stable dispersion state.
Furthermore, when these nanoparticles were freeze-dried and then redispersed in water, a slightly increased particle size (130 to 150 nm) and a good dispersion of nanoparticles were obtained.
（実施例３：カーボンナノホーンをコアとして蛍光を示すナノ粒子の作成）
カーボンナノホーンを１００ｍｇ、下記の式（化３）で示される蛍光物質を３０ｍｇ、上記両親媒性化合物１を１００ｇ、量り取り、蒸留水１Ｌを加えた。この混合物をホモジナイザーで３０分撹拌した後、アルティマイザーに投入し、圧力２４５ＭＰａで１００パスし、両親媒性化合物でコーティングされたナノ粒子の水分散液を得た。
また、このナノ粒子の水分散液を凍結乾燥した試料について透過型電子顕微鏡観察をおこなったところ、カーボンナノホーン１次粒子に相当するサイズ、形状の粒子が観測され、コーティングによって１次粒子のサイズ、形状が変化しないことが確認された（図３）。
(Example 3: Creation of nanoparticles exhibiting fluorescence using a carbon nanohorn as a core)
100 mg of carbon nanohorn, 30 mg of a fluorescent substance represented by the following formula (Chemical Formula 3), 100 g of the amphiphilic compound 1 were weighed out, and 1 L of distilled water was added. The mixture was stirred with a homogenizer for 30 minutes and then charged into an optimizer and passed for 100 passes at a pressure of 245 MPa to obtain an aqueous dispersion of nanoparticles coated with an amphiphilic compound.
In addition, when a sample obtained by freeze-drying the aqueous dispersion of nanoparticles was observed with a transmission electron microscope, particles having a size and shape corresponding to the primary particles of carbon nanohorn were observed. It was confirmed that the shape did not change (FIG. 3).
（実施例４：マグネタイトをコアとするナノ粒子の作成）
マグネタイト（一次粒径２０〜２０ｎｍ）を２５０ｍｇ、上記両親媒化合物１を２５０ｍｇ、量り取り、蒸留水１Ｌを加えた。この混合物をホモジナイザーで３０分撹拌した後、アルティマイザーに投入し、圧力２４５ＭＰａで１００パスし、両親媒性化合物でコーティングされたナノ粒子の水分散液を得た。動的光散乱ではパス数の増大ともに粒径の減少が観察され、２５パスで一次粒径の粒子サイズ（２５ｎｍ）となり、それ以上のパス数では逆に粒子サイズが増大した。このナノ粒子水分散液はその後１週間以上沈殿を生じず、安定な分散状態を保った。
このナノ粒子の水分散液を凍結乾燥した試料について透過型電子顕微鏡観察をおこなったところ、マグネタイト１次粒子に相当するサイズ、形状の粒子が観測され、コーティングによって１次粒子のサイズ、形状が変化しないことが確認された（図４）。
(Example 4: Creation of nanoparticles having magnetite as a core)
250 mg of magnetite (primary particle size 20 to 20 nm) and 250 mg of the amphiphilic compound 1 were weighed out and 1 L of distilled water was added. The mixture was stirred with a homogenizer for 30 minutes and then charged into an optimizer and passed for 100 passes at a pressure of 245 MPa to obtain an aqueous dispersion of nanoparticles coated with an amphiphilic compound. In dynamic light scattering, a decrease in particle size was observed with an increase in the number of passes, and the particle size of the primary particle size (25 nm) was obtained in 25 passes, and conversely the particle size was increased in more passes. This nanoparticle aqueous dispersion did not precipitate for more than one week thereafter, and maintained a stable dispersion state.
When a sample obtained by lyophilizing the aqueous dispersion of nanoparticles was observed with a transmission electron microscope, particles having a size and shape corresponding to magnetite primary particles were observed, and the size and shape of the primary particles were changed by coating. It was confirmed that it does not (FIG. 4).
（実施例５：酸化亜鉛をコアとするナノ粒子の作成）
酸化亜鉛（一次粒径５０〜７０ｎｍ）２５０ｍｇ、両親媒化合物５０ｍｇをはかりとり、蒸留水１Ｌを加えた。この混合物をホモジナイザーで３０分撹拌した後、アルティマイザーに投入し、圧力２４５ＭＰａで１００パスし、両親媒性化合物でコーティングされたナノ粒子の水分散液を得た。動的光散乱ではパス数の増大ともに粒径の減少が観察され、５０パスで一次粒径の粒子サイズ（５０ｎｍ）となり、それ以上のパス数では逆に粒子サイズが増大した。このナノ粒子水分散液はその後１週間以上沈殿を生じず、安定な分散状態を保った。
このナノ粒子の水分散液を凍結乾燥した試料について透過型電子顕微鏡観察をおこなったところ、酸化亜鉛１次粒子に相当するサイズ、形状の粒子が観測され、コーティングによって１次粒子のサイズ、形状が変化しないことが確認された（図５）。
(Example 5: Preparation of nanoparticles having zinc oxide as a core)
Zinc oxide (primary particle size 50 to 70 nm) 250 mg and amphiphile compound 50 mg were weighed and 1 L of distilled water was added. The mixture was stirred with a homogenizer for 30 minutes and then charged into an optimizer and passed for 100 passes at a pressure of 245 MPa to obtain an aqueous dispersion of nanoparticles coated with an amphiphilic compound. In dynamic light scattering, a decrease in particle size was observed with an increase in the number of passes, the particle size of the primary particle size (50 nm) was reached at 50 passes, and the particle size was increased at higher passes. This nanoparticle aqueous dispersion did not precipitate for more than one week thereafter, and maintained a stable dispersion state.
When a sample obtained by freeze-drying the aqueous dispersion of nanoparticles was observed with a transmission electron microscope, particles having a size and shape corresponding to zinc oxide primary particles were observed, and the size and shape of the primary particles were determined by coating. It was confirmed that there was no change (FIG. 5).
（実施例６：超音波ホモジナイザーを用いて作成した酸化チタンをコアとするナノ粒子の作成）
石原産業製酸化チタンＳＴ−０１(平均粒径５ｎｍ)、ＳＴ−２１(平均粒径２３ｎｍ)、ＳＴ−４１(平均粒径１５４ｎｍ)を、それぞれ１０ｍｇ、両親媒性化合物として、両親媒性化合物１、及び両親媒性化合物２、比較例として、Tween80、ＳＤＳ）を１０ｍｇ、量り取り、蒸留水４０ｍＬを加えた。この混合物をプローブ式超音波発生装置による超音波照射をおこなった(１２０Ｗ)。この際、液温が６０℃C以上になるのを確認し、その後、室温まで放冷し、両親媒性化合物でコーティングされたナノ粒子の水分散液を得た。
動的光散乱ではＳＤＳの場合を除き、超音波照射１０分以後の大きな粒径変化は認められなかった。さらにこのナノ粒子を凍結乾燥後、水に再分散し、この分散液について動的光散乱による粒径測定を行なった。
以下に結果を示す。
(Example 6: Production of nanoparticles having titanium oxide as a core produced using an ultrasonic homogenizer)
Ishihara Sangyo Titanium Oxide ST-01 (average particle size 5 nm), ST-21 (average particle size 23 nm), ST-41 (average particle size 154 nm) 10 mg each as amphiphilic compound, amphiphilic compound 1 , And Amphiphilic Compound 2, as a comparative example, 10 mg of Tween 80, SDS) was weighed out and 40 mL of distilled water was added. This mixture was subjected to ultrasonic irradiation with a probe type ultrasonic generator (120 W). At this time, it was confirmed that the liquid temperature became 60 ° C. or higher, and then allowed to cool to room temperature to obtain an aqueous dispersion of nanoparticles coated with an amphiphilic compound.
In dynamic light scattering, except for SDS, no large particle size change was observed after 10 minutes of ultrasonic irradiation. Further, the nanoparticles were lyophilized and then redispersed in water, and the particle size of the dispersion was measured by dynamic light scattering.
The results are shown below.
上記の表から明らかなように、本発明の両親媒性化合物１及び２を用いた場合、ナノ微粒子は、２週間程度で沈殿するものの、振とうすると再び分散するのに対して、Tween80やＳＤＳの沈殿物は大きな凝集体となっており、振とうしてもすぐに沈殿する。 As is apparent from the above table, when the amphiphilic compounds 1 and 2 of the present invention are used, the nanoparticle precipitates in about 2 weeks, but disperses again when shaken, whereas Tween80 and SDS The precipitate is a large agglomerate and immediately precipitates upon shaking.
炭素材料ナノ粒子はインク、ＤＤＳ材料としての応用が期待されている一方、単体では極めて水分散性が悪い。本発明により、水に良く分散し、かつ乾燥、再分散可能にすることで、有機溶媒フリーなインク、またＤＤＳ材料としての応用研究が大いに進む可能性がある。また、金属酸化物や金属硫化物ナノ粒子は、量子ドット、ＤＤＳ、磁気医療やバイオセンサ材料として有望であり、容易に水分散を可能にすることで材料光学、医療分野で大きくこれらの粒子の適用範囲を広げると期待できる。 While carbon material nanoparticles are expected to be used as inks and DDS materials, they are extremely poor in water dispersibility when used alone. By making the present invention well dispersed in water and drying and redispersing, application research as an organic solvent-free ink and a DDS material may greatly advance. In addition, metal oxide and metal sulfide nanoparticles are promising as quantum dots, DDS, magnetic medicine and biosensor materials, and can easily disperse in water, so that in the field of material optics and medicine, It can be expected to expand the application range.
Claims (4)
下記一般式（１）
Ｇ−ＮＨＣＯ−Ｒ １ （１）
（式中、Ｇは糖のアノマー炭素原子に結合するヘミアセタール水酸基を除いた糖残基を表し、Ｒ １ は炭素数が１０〜２４の不飽和炭化水素基を表す。）
で表わされるＮ−グリコシド型糖脂質、
下記一般式（２）
Ｒ ２ ＣＯ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＯＨ (２)
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質、又は
下記一般式（３）
Ｈ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＮＨＲ ２ （３）
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質、
のいずれかであることを特徴とする易分散性ナノ粒子。 The surface of the nanoparticles, gels - liquid crystal phase transition temperature is higher than room temperature, and a readily dispersible nanoparticles comprising coated with a crystalline material consisting of lower than the boiling point of water amphiphilic compound, the amphiphilic Compound is
The following general formula (1)
G-NHCO-R 1 (1)
(In the formula, G represents a sugar residue excluding the hemiacetal hydroxyl group bonded to the anomeric carbon atom of the sugar, and R 1 represents an unsaturated hydrocarbon group having 10 to 24 carbon atoms.)
N-glycoside type glycolipid represented by
The following general formula (2)
R 2 CO (NH-CHR 3 -CO) m OH (2)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by:
The following general formula (3)
H (NH—CHR 3 —CO) m NHR 2 (3)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by
An easily dispersible nanoparticle characterized by being one of the following .
ゲル−液晶相転移温度が室温より高く、かつ水の沸点より低い両親媒性化合物からなる結晶性物質を有効成分とし、前記両親媒性化合物が、
下記一般式（１）
Ｇ−ＮＨＣＯ−Ｒ １ （１）
（式中、Ｇは糖のアノマー炭素原子に結合するヘミアセタール水酸基を除いた糖残基を表し、Ｒ １ は炭素数が１０〜２４の不飽和炭化水素基を表す。）
で表わされるＮ−グリコシド型糖脂質、
下記一般式（２）
Ｒ ２ ＣＯ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＯＨ (２)
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表されるペプチド脂質、又は
下記一般式（３）
Ｈ（ＮＨ−ＣＨＲ ３ −ＣＯ） ｍ ＮＨＲ ２ （３）
（式中、Ｒ ２ は炭素数１０〜２４の炭化水素基、Ｒ ３ はアミノ酸側鎖、ｍは１〜３の整数を表す。）
で表わされるペプチド脂質、
のいずれかであることを特徴とするナノ粒子用分散剤。 A dispersant for dispersing nanoparticles in water by coating their surfaces ,
A crystalline substance composed of an amphiphilic compound having a gel-liquid crystal phase transition temperature higher than room temperature and lower than the boiling point of water is an active ingredient, and the amphiphilic compound is:
The following general formula (1)
G-NHCO-R 1 (1)
(In the formula, G represents a sugar residue excluding the hemiacetal hydroxyl group bonded to the anomeric carbon atom of the sugar, and R 1 represents an unsaturated hydrocarbon group having 10 to 24 carbon atoms.)
N-glycoside type glycolipid represented by
The following general formula (2)
R 2 CO (NH-CHR 3 -CO) m OH (2)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by:
The following general formula (3)
H (NH—CHR 3 —CO) m NHR 2 (3)
(In the formula, R 2 represents a hydrocarbon group having 10 to 24 carbon atoms, R 3 represents an amino acid side chain, and m represents an integer of 1 to 3).
A peptide lipid represented by
Dispersants for nanoparticles characterized by either der Rukoto of.
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