JP2015067616A - Manufacturing method of polylactic acid microparticles, and polylactic acid microparticles - Google Patents
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Abstract
Description
本発明は、ポリ乳酸微粒子の製造方法及びポリ乳酸微粒子に関する。 The present invention relates to a method for producing polylactic acid fine particles and polylactic acid fine particles.
化石燃料から製造される樹脂微粒子は、表面積が大きいことにより、種々の機能を発現する。このような樹脂微粒子は、近年、化粧品パウダー、塗料等、多くの技術分野において利用されている（特許文献１参照）。 Resin particles produced from fossil fuels exhibit various functions due to their large surface area. In recent years, such resin fine particles have been used in many technical fields such as cosmetic powders and paints (see Patent Document 1).
樹脂微粒子を含む製品を廃棄する際、樹脂微粒子を回収することはほぼ不可能であり、樹脂微粒子はそのまま環境中に流出されている。化石燃料から製造される樹脂微粒子は生分解されにくいため、流出された樹脂微粒子は環境面での負荷となる。 When a product containing resin fine particles is discarded, it is almost impossible to collect the resin fine particles, and the resin fine particles are discharged into the environment as they are. Since resin fine particles produced from fossil fuel are difficult to be biodegraded, the discharged resin fine particles become an environmental load.
ところで、ポリ乳酸は、バイオマスであり、かつ生分解性を有するため、化石燃料から製造される樹脂微粒子の代わりにポリ乳酸微粒子を用いれば、環境面での負荷を軽減できる。しかしながら、ポリ乳酸微粒子を容易に製造する方法は知られていない。 By the way, since polylactic acid is a biomass and has biodegradability, if polylactic acid fine particles are used instead of resin fine particles produced from fossil fuel, the environmental load can be reduced. However, a method for easily producing polylactic acid fine particles is not known.
本発明は以上の点に鑑みなされたものであり、ポリ乳酸微粒子を容易に製造できる製造方法及びポリ乳酸微粒子を提供することを目的とする。 This invention is made | formed in view of the above point, and it aims at providing the manufacturing method and polylactic acid microparticles | fine-particles which can manufacture a polylactic acid microparticles | fine-particles easily.
本発明のポリ乳酸微粒子の製造方法は、ポリ乳酸を第１の溶媒に溶解した溶液に、前記第１の溶媒よりポリ乳酸の溶解度が低い第２の溶媒を加え、ポリ乳酸微粒子を析出させることを特徴とする。 In the method for producing polylactic acid fine particles of the present invention, a second solvent having a polylactic acid solubility lower than that of the first solvent is added to a solution in which polylactic acid is dissolved in a first solvent, thereby precipitating polylactic acid fine particles. It is characterized by.
本発明によれば、ポリ乳酸微粒子を容易に製造することができる。本発明で製造するポリ乳酸微粒子は、例えば、カードハウス構造等の機能構造を有する微粒子とすることができる。ここで、機能構造とは、何らかの機能を発現する構造を意味する。 According to the present invention, polylactic acid fine particles can be easily produced. The polylactic acid fine particles produced in the present invention can be fine particles having a functional structure such as a card house structure. Here, the functional structure means a structure that expresses some function.
本発明のポリ乳酸微粒子は、カードハウス構造を有する。そのため、ポリ乳酸微粒子の表面積が非常に大きくなり、例えば、皮脂の吸着や光散乱能等の用途において優れた特性を有する。 The polylactic acid fine particles of the present invention have a card house structure. Therefore, the surface area of the polylactic acid fine particles becomes very large, and has excellent characteristics in applications such as sebum adsorption and light scattering ability.
本発明の実施形態を説明する。ポリ乳酸は、乳酸がエステル結合により重合した化合物である。ポリ乳酸の分子量は、５万〜２０万の範囲が好適である。ポリ乳酸としては、例えば、市販品（例えば、株式会社武蔵野化学研究所製のPLA AL lot No.PLL10529等）を用いることができる。また、ポリ乳酸は、例えば、植物（例えば、トウモロコシ、イモ類、ビート、サトウキビ等）から取り出したデンプンを発酵することで乳酸を得て、その乳酸を重合させて製造することができる。ポリ乳酸を構成する乳酸は、L体であってもよいし、Ｄ体であってもよいし、両者が混在していてもよい。 An embodiment of the present invention will be described. Polylactic acid is a compound obtained by polymerizing lactic acid through an ester bond. The molecular weight of polylactic acid is preferably in the range of 50,000 to 200,000. As polylactic acid, for example, a commercially available product (for example, PLA AL lot No. PLL10529 manufactured by Musashino Chemical Laboratory Co., Ltd.) can be used. Polylactic acid can be produced, for example, by fermenting starch extracted from a plant (for example, corn, potatoes, beet, sugarcane, etc.) to obtain lactic acid and polymerizing the lactic acid. Lactic acid constituting polylactic acid may be L-form, D-form, or a mixture of both.
製造するポリ乳酸微粒子の粒径は、例えば、２〜２０μｍとすることができる。なお、この粒径は、電子顕微鏡観察、コールターカウンター、あるいは光散乱法等の方法で測定した値である。 The particle diameter of the polylactic acid fine particles to be produced can be set to 2 to 20 μm, for example. The particle size is a value measured by a method such as electron microscope observation, Coulter counter, or light scattering method.
第１の溶媒としては、ポリ乳酸を溶解可能なものを適宜選択して用いることができる。第１の溶媒としては、例えば、クロロフォルム、ブロモホルム、塩化メチレン、１，２−ジクロロエタン、１，１，１−トリクロロエタン、クロロベンゼン、２，６−ジクロロトルエン等の炭化水素系溶媒の他、各種エステル系溶媒、ケトン系溶媒、カルボン酸系溶媒等が挙げられる。 As the first solvent, a solvent capable of dissolving polylactic acid can be appropriately selected and used. Examples of the first solvent include hydrocarbon solvents such as chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, and various ester-based solvents. A solvent, a ketone solvent, a carboxylic acid solvent, etc. are mentioned.
第２の溶媒を加える前の溶液におけるポリ乳酸の濃度は、２．５〜２．８ｗｔ％の範囲が好ましい。この範囲内であることにより、ポリ乳酸微粒子が一層生成し易くなる。
第２の溶媒としては、第１の溶媒よりもポリ乳酸の溶解度が低い溶媒を適宜選択して用いることができる。第２の溶媒としては、例えば、エタノール、メタノール、イソプロピルアルコール等が挙げられる。
The concentration of polylactic acid in the solution before adding the second solvent is preferably in the range of 2.5 to 2.8 wt%. By being within this range, polylactic acid fine particles are more easily generated.
As the second solvent, a solvent having a polylactic acid solubility lower than that of the first solvent can be appropriately selected and used. Examples of the second solvent include ethanol, methanol, isopropyl alcohol, and the like.
溶液の温度は、例えば、第２の溶媒を加える前、及び加えた後において、それぞれ、常温（例えば２５℃）とすることができる。また、ポリ乳酸微粒子の製造方法における一部又は全部の工程において、適宜、溶液の温度を調整（例えば加温又は冷却）してもよい。 The temperature of the solution can be, for example, normal temperature (for example, 25 ° C.) before and after the addition of the second solvent. Further, in some or all of the steps in the method for producing polylactic acid fine particles, the temperature of the solution may be appropriately adjusted (for example, heated or cooled).
第２の溶媒の添加量は、第２の溶媒を加えた後の溶液におけるポリ乳酸の濃度（以下、添加後濃度とする）が１．６５〜２．３０（好ましくは１．７０〜１．８０）ｗｔ％の範囲内となる量が好ましい。添加後濃度が１．６５ｗｔ％以上（好ましくは１．７０ｗｔ％以上）である場合、第２の溶媒を添加した後の溶液にポリ乳酸微粒子の凝集体が析出し難い。また、添加後濃度が２．３０ｗｔ％以下（好ましくは１．８０ｗｔ％以下）である場合、ポリ乳酸微粒子が溶液中に生成し易い。 The amount of the second solvent added is such that the concentration of polylactic acid in the solution after adding the second solvent (hereinafter referred to as the concentration after addition) is 1.65 to 2.30 (preferably 1.70 to 1.30). 80) An amount that falls within the range of wt% is preferred. When the concentration after addition is 1.65 wt% or more (preferably 1.70 wt% or more), aggregates of polylactic acid fine particles are difficult to precipitate in the solution after addition of the second solvent. Further, when the concentration after addition is 2.30 wt% or less (preferably 1.80 wt% or less), polylactic acid fine particles are likely to be generated in the solution.
第２の溶媒の添加後、例えば、溶液を攪拌することができる。攪拌することにより、ポリ乳酸微粒子の凝集を軽減することができる。攪拌の手段としては、例えば、撹拌子、撹拌翼、ディスペンサー等を用いることができる。例えば、上記の攪拌後、溶液を静置することで、ポリ乳酸微粒子を沈殿させることができる。 After the addition of the second solvent, for example, the solution can be stirred. Agitation of the polylactic acid fine particles can be reduced by stirring. As a stirring means, for example, a stirring bar, a stirring blade, a dispenser, or the like can be used. For example, the polylactic acid fine particles can be precipitated by allowing the solution to stand after the stirring.
溶液中で析出したポリ乳酸微粒子は、周知の方法（例えば吸引濾過や溶媒蒸発等）により溶媒と分離し、取り出すことができる。
本発明のポリ乳酸微粒子は、例えば、上述した製造方法で製造できる。本発明のポリ乳酸微粒子は、カードハウス構造を有する。そのため、ポリ乳酸微粒子の表面積が非常に大きくなり、例えば、皮脂の吸着や光散乱能等の用途において優れた特性を有する。なお、カードハウス構造とは、特許第３６９６４１５号公報、特許第２６２１１４５号公報等に記載されたものであり、トランプのカードが重なり合った様な構造を意味する。
The polylactic acid fine particles precipitated in the solution can be separated from the solvent by a known method (for example, suction filtration or solvent evaporation) and taken out.
The polylactic acid fine particles of the present invention can be produced, for example, by the production method described above. The polylactic acid fine particles of the present invention have a card house structure. Therefore, the surface area of the polylactic acid fine particles becomes very large, and has excellent characteristics in applications such as sebum adsorption and light scattering ability. The card house structure is described in Japanese Patent No. 3696415, Japanese Patent No. 2621145, and the like, and means a structure in which cards of cards are overlapped.
本発明のポリ乳酸微粒子は、ポリ乳酸のみから成っていてもよいし、ポリ乳酸とともに、他の成分を含んでいてもよい。また、本発明のポリ乳酸微粒子は、表面の一部又は全部を、ポリ乳酸以外の成分から成る層で覆われていてもよい。
（実施例）
１．ポリ乳酸微粒子の製造方法
常温下で、ポリ乳酸をクロロフォルム（第１の溶媒の一実施形態）に溶解し、ポリ乳酸のクロロフォルム溶液（以下、ポリ乳酸溶液とする）を調製した。このとき、ポリ乳酸として、株式会社武蔵野化学研究所製のPLA AL lot No.PLL10529を用いた。また、ポリ乳酸溶液におけるポリ乳酸の濃度は、２．７ｗｔ％とした。
The polylactic acid fine particles of the present invention may be composed only of polylactic acid or may contain other components together with polylactic acid. Moreover, the polylactic acid microparticles | fine-particles of this invention may be covered with the layer which consists of components other than polylactic acid, part or all of the surface.
(Example)
1. Production Method of Polylactic Acid Fine Particles Polylactic acid was dissolved in chloroform (one embodiment of the first solvent) at room temperature to prepare a polylactic acid chloroform solution (hereinafter referred to as polylactic acid solution). At this time, PLA AL lot No. PLL10529 manufactured by Musashino Chemical Laboratory, Inc. was used as polylactic acid. The concentration of polylactic acid in the polylactic acid solution was 2.7 wt%.
次に、常温下で、ポリ乳酸溶液にエタノール（第２の溶媒の一実施形態）を添加した。添加後の溶液におけるポリ乳酸濃度は１．７４ｗｔ％であった。エタノールの添加後、溶液中に白濁、凝集体が形成された。この凝集体は、析出したポリ乳酸微粒子の凝集体である。 Next, ethanol (an embodiment of the second solvent) was added to the polylactic acid solution at room temperature. The polylactic acid concentration in the solution after the addition was 1.74 wt%. After the addition of ethanol, white turbidity and aggregates were formed in the solution. This aggregate is an aggregate of precipitated polylactic acid fine particles.
次に、攪拌子を用いて、３０分間、溶液を攪拌した。この攪拌により、溶液中の凝集体が分散した。攪拌終了後、溶液を１日静置すると、ポリ乳酸微粒子の沈殿が生じた。その後、吸引濾過により、沈殿したポリ乳酸微粒子を分離し、乾燥させた。 Next, the solution was stirred for 30 minutes using a stirring bar. By this stirring, aggregates in the solution were dispersed. When the solution was allowed to stand for 1 day after the completion of stirring, polylactic acid fine particles were precipitated. Thereafter, the precipitated polylactic acid fine particles were separated by suction filtration and dried.
２．ポリ乳酸微粒子の評価
上述した製造方法で得られたポリ乳酸微粒子をカーボンテープに貼り付け、６０秒間スパッタリングをした後、電子顕微鏡（ＳＥＭ）観察を行った。なお、スパッタリングは、ＳＥＭ観察中にポリ乳酸微粒子が溶けることを防止するための処理である。
2. Evaluation of polylactic acid fine particles The polylactic acid fine particles obtained by the production method described above were attached to a carbon tape, sputtered for 60 seconds, and then observed with an electron microscope (SEM). Sputtering is a process for preventing the polylactic acid fine particles from melting during SEM observation.
観察時に撮影したＳＥＭ写真を図１Ａ、１Ｂに示す。この写真から、直径１０μｍ程度のポリ乳酸微粒子が得られたことが確認できた。また、ポリ乳酸微粒子がカードハウス構造を有することが確認できた。 SEM photographs taken during observation are shown in FIGS. 1A and 1B. From this photograph, it was confirmed that polylactic acid fine particles having a diameter of about 10 μm were obtained. It was also confirmed that the polylactic acid fine particles had a card house structure.
３．ポリ乳酸微粒子の製造方法が奏する効果
（１）本実施例の製造方法によれば、生分解性高分子から成るポリ乳酸微粒子を容易に製造することができる。
3. Effects produced by the method for producing polylactic acid fine particles (1) According to the production method of this example, polylactic acid fine particles comprising a biodegradable polymer can be produced easily.
（２）製造されたポリ乳酸微粒子はカードハウス構造を有し、その表面積が非常に大きいため、例えば、皮脂の吸着や光散乱能等の用途において優れた特性を有する。
（３）本実施例の製造方法では、揮発性でない有機溶媒を使用しないため、溶媒除去が容易である。
(2) The produced polylactic acid fine particles have a card house structure and a very large surface area, and thus have excellent characteristics in applications such as sebum adsorption and light scattering ability.
(3) Since the non-volatile organic solvent is not used in the manufacturing method of this example, the solvent can be easily removed.
（４）ポリ乳酸微粒子は生分解性を有するため、環境面での負荷を軽減できる。
（５）ポリ乳酸微粒子自身がアンチエイジング機能を有している。
（参考例１）
基本的には前記実施例と同様の方法であるが、エタノールの添加量を変えることで、エタノール添加後の溶液におけるポリ乳酸の濃度を１．５９〜１．６９ｗｔ％として、ポリ乳酸微粒子を製造した。この場合、エタノール添加後に生じた凝集体が、攪拌後も一部残っていた。
(参考例２)
前記実施例と同様にポリ乳酸溶液を調製し、そのポリ乳酸溶液にエタノールを添加した。ただし、エタノール添加後の溶液におけるポリ乳酸の濃度は２．３０ｗｔ％とした。この場合、エタノール添加後の溶液中に、ポリ乳酸微粒子が析出しなかった。
(4) Since the polylactic acid fine particles are biodegradable, the environmental load can be reduced.
(5) The polylactic acid fine particles themselves have an anti-aging function.
(Reference Example 1)
Basically, the method is the same as in the above example, but by changing the amount of ethanol added, the concentration of polylactic acid in the solution after ethanol addition was changed to 1.59 to 1.69 wt% to produce polylactic acid fine particles. did. In this case, a part of the aggregate formed after the addition of ethanol remained even after stirring.
(Reference example 2)
A polylactic acid solution was prepared in the same manner as in the previous example, and ethanol was added to the polylactic acid solution. However, the concentration of polylactic acid in the solution after addition of ethanol was 2.30 wt%. In this case, polylactic acid fine particles did not precipitate in the solution after addition of ethanol.
尚、本発明は前記実施の形態になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。
例えば、前記実施例において、クロロフォルムの代わりに、適宜選択した他の溶媒を用いても略同様の効果を奏することができる。
In addition, this invention is not limited to the said embodiment at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from this invention.
For example, in the above-described embodiment, substantially the same effect can be obtained by using other appropriately selected solvents instead of chloroform.
また、前記実施例において、エタノールの代わりに、適宜選択した他の溶媒を用いても略同様の効果を奏することができる。
また、前記実施例において、他のポリ乳酸（例えば、製造方法、分子量、光学異性体の比率等が異なるもの）を用いてもよい。
Moreover, in the said Example, the substantially same effect can be show | played even if it uses the other solvent selected suitably instead of ethanol.
Moreover, in the said Example, you may use other polylactic acid (For example, a manufacturing method, molecular weight, the ratio of an optical isomer, etc. differ).
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| WO2011142283A1 (en) * | 2010-05-10 | 2011-11-17 | 国立大学法人群馬大学 | Method for producing polylactic acid microparticles, polylactic acid microparticles, and crystal nucleation agent, molded article, and surface modifier using the same |
| WO2012105140A1 (en) * | 2011-01-31 | 2012-08-09 | 東レ株式会社 | Method for producing microparticles of polylactic acid-based resin, microparticles of polylactic acid-based resin and cosmetic using same |
| JP2013133473A (en) * | 2011-12-26 | 2013-07-08 | Toray Ind Inc | Method for producing polylactic acid-based resin fine particle |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180063076A (en) | 2015-09-30 | 2018-06-11 | 세키스이가세이힝코교가부시키가이샤 | Porous resin fine particles and manufacturing method thereof |
| US11548995B2 (en) | 2015-09-30 | 2023-01-10 | Sekisui Plastics Co., Ltd. | Porous resin microparticles and manufacturing method for same |
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