JP5703517B2 - Zinc oxide crystal production method, zinc oxide crystal - Google Patents
Zinc oxide crystal production method, zinc oxide crystal Download PDFInfo
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- JP5703517B2 JP5703517B2 JP2011055522A JP2011055522A JP5703517B2 JP 5703517 B2 JP5703517 B2 JP 5703517B2 JP 2011055522 A JP2011055522 A JP 2011055522A JP 2011055522 A JP2011055522 A JP 2011055522A JP 5703517 B2 JP5703517 B2 JP 5703517B2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 166
- 239000011787 zinc oxide Substances 0.000 title claims description 83
- 239000013078 crystal Substances 0.000 title claims description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000003945 anionic surfactant Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 23
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- 230000003020 moisturizing effect Effects 0.000 claims description 11
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- 230000029663 wound healing Effects 0.000 claims description 9
- 239000003093 cationic surfactant Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 206010052428 Wound Diseases 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000516 sunscreening agent Substances 0.000 description 4
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 3
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229960000458 allantoin Drugs 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002674 hyaluronan Polymers 0.000 description 3
- 229960003160 hyaluronic acid Drugs 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003357 wound healing promoting agent Substances 0.000 description 2
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は酸化亜鉛結晶の生成方法、及びこれにより生成される酸化亜鉛結晶に関する。 The present invention relates to a method for producing zinc oxide crystals and a zinc oxide crystal produced thereby.
酸化亜鉛は、紫外線吸収剤、創傷治療剤、光触媒などの材料として、多岐にわたる分野で用いられている。また、ｐＨ値を調整したり、有機物を添加したりすることで様々な形状の酸化亜鉛結晶を生成可能であることが可能である。 Zinc oxide is used in various fields as a material for ultraviolet absorbers, wound healing agents, photocatalysts and the like. In addition, it is possible to generate zinc oxide crystals of various shapes by adjusting the pH value or adding an organic substance.
例えば、特許文献１においては、亜鉛イオンとアミン化合物を含むｐＨ７以上の水溶液に基材を浸漬することによって、基材上に結晶形状が花状の酸化亜鉛結晶を自己組織的に析出させる方法が開示されている。 For example, in Patent Document 1, there is a method in which zinc oxide crystals having a flower shape are self-organized on a substrate by immersing the substrate in an aqueous solution containing zinc ions and an amine compound and having a pH of 7 or higher. It is disclosed.
また、特許文献２においては、亜鉛化合物水溶液とアミン化合物とを混合し、混合水溶液のｐＨを７以上として沈殿物を析出させ、さらに水溶液を４０℃以上に加熱することによって、マイクロスケールの針状形状を有する酸化亜鉛粒子や花びら形状を有する酸化亜鉛集積体などを製造する方法が開示されている。 Moreover, in patent document 2, a zinc compound aqueous solution and an amine compound are mixed, the pH of the mixed aqueous solution is set to 7 or more to precipitate a precipitate, and the aqueous solution is further heated to 40 ° C. or more to obtain a microscale needle-like shape. Methods for producing zinc oxide particles having a shape, zinc oxide aggregates having a petal shape, and the like are disclosed.
しかしながら、従来技術においては、酸化亜鉛結晶の形状に関してマイクロスケールでの制御が主であり、ナノスケールでの制御については報告されていなかった。そこで、本発明者は、マイクロスケールで制御された酸化亜鉛結晶に対して、薬物成分などを保持することが可能なナノスケールの構造を同時に付与することを目的として研究を行った。その結果、アニオン性界面活性剤の存在下においては、マイクロスケールの板状の酸化亜鉛結晶を生成することが可能であり、同時に薬物成分などを保持することが可能なナノスケールの構造を付与することが可能であることがわかった。 However, in the prior art, the control on the microscale is mainly performed on the shape of the zinc oxide crystal, and the control on the nanoscale has not been reported. Therefore, the present inventor conducted research for the purpose of simultaneously imparting a nanoscale structure capable of retaining drug components and the like to zinc oxide crystals controlled on a microscale. As a result, in the presence of an anionic surfactant, it is possible to produce microscale plate-like zinc oxide crystals, and at the same time impart a nanoscale structure capable of retaining drug components and the like. It turns out that it is possible.
本発明は、アニオン性界面活性剤を含む水溶液に亜鉛イオンを加えることでアニオン性界面活性剤層と酸化亜鉛層とからなる多層構造を有する酸化亜鉛結晶を生成する酸化亜鉛結晶の生成方法などを提案する。また、アニオン性界面活性剤を含む水溶液に亜鉛イオンを加えることで板状の酸化亜鉛結晶を生成する酸化亜鉛結晶の生成方法などを提案する。 The present invention relates to a method for producing a zinc oxide crystal, which produces a zinc oxide crystal having a multilayer structure composed of an anionic surfactant layer and a zinc oxide layer by adding zinc ions to an aqueous solution containing an anionic surfactant. suggest. Moreover, the production | generation method of the zinc oxide crystal | crystallization etc. which produce | generate a plate-shaped zinc oxide crystal | crystallization by adding zinc ion to the aqueous solution containing an anionic surfactant are proposed.
本発明の生成方法により生成される酸化亜鉛結晶は、アニオン性界面活性剤と酸化亜鉛層とからなるナノスケールの多層構造を有するため、当該多層構造の内部に肌の保湿成分や創傷治療成分を内包することが可能になる。これにより、酸化亜鉛の効果に加えて内包成分の効果を同時に発揮することが可能になる。また、全体としてマイクロスケールの板状構造となっているため、針状形状や球状形状などの酸化亜鉛結晶に比べて紫外線などの光を吸収する実効面積が大きく、優れたサンスクリーン剤などの材料として用いることが可能になる。 Since the zinc oxide crystal produced by the production method of the present invention has a nanoscale multilayer structure composed of an anionic surfactant and a zinc oxide layer, the skin moisturizing component and wound healing component are contained inside the multilayer structure. It can be included. Thereby, in addition to the effect of zinc oxide, the effect of the inclusion component can be exhibited simultaneously. In addition, since it has a microscale plate-like structure as a whole, it has a large effective area for absorbing light such as ultraviolet rays compared to zinc oxide crystals such as needles and spheres, and is an excellent material such as a sunscreen agent. Can be used.
以下、本件発明の実施の形態について、添付図面を用いて説明する。なお、本件発明は、これら実施形態に何ら限定されるべきものではなく、その要旨を逸脱しない範囲において、種々なる態様で実施し得る。
<実施形態：概要>
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, this invention should not be limited to these embodiments at all, and can be implemented in various modes without departing from the gist thereof.
<Embodiment: Overview>
本発明の生成方法により生成される酸化亜鉛結晶は、全体としてマイクロスケールの板状構造となっており、同時にアニオン性界面活性剤と酸化亜鉛層とからなるナノスケールの多層構造を備える。 The zinc oxide crystal produced by the production method of the present invention has a microscale plate-like structure as a whole, and at the same time has a nanoscale multilayer structure comprising an anionic surfactant and a zinc oxide layer.
<酸化亜鉛結晶の生成・抽出>
本発明の酸化亜鉛結晶は、アニオン性界面活性剤を含んだ水溶液に亜鉛イオンを加え、撹拌処理を行うといった簡便な手法によって、生成することが可能である。
<Formation and extraction of zinc oxide crystals>
The zinc oxide crystal of the present invention can be produced by a simple method of adding zinc ions to an aqueous solution containing an anionic surfactant and stirring the solution.
図１は、酸化亜鉛結晶の生成・抽出方法の処理の流れの一例を示す図である。まずステップＳ０１０１において、アニオン性界面活性剤をイオン交換水に溶解させ、水溶液がアルカリ性となるようにｐＨ調整剤を添加する。次にステップＳ０１０２において、ステップＳ０１０１にて得られた水溶液に対して亜鉛イオンを加え、撹拌する。次にステップＳ０１０３において、ステップＳ０１０２にて得られた撹拌後の混合溶液をろ過・洗浄して、固液分離する。次にステップＳ０１０４において、ステップＳ０１０３にて得られた粒子を乾燥させる。以上の処理を経ることによって、酸化亜鉛結晶の生成と抽出を行うことが可能になる。 FIG. 1 is a diagram illustrating an example of a processing flow of a method for generating and extracting zinc oxide crystals. First, in step S0101, an anionic surfactant is dissolved in ion-exchanged water, and a pH adjuster is added so that the aqueous solution becomes alkaline. Next, in step S0102, zinc ions are added to the aqueous solution obtained in step S0101, and stirred. Next, in step S0103, the mixed solution after stirring obtained in step S0102 is filtered and washed to perform solid-liquid separation. Next, in step S0104, the particles obtained in step S0103 are dried. Through the above treatment, it is possible to generate and extract zinc oxide crystals.
イオン交換水に溶解させるアニオン性界面活性剤としては、長鎖アルキル鎖を有し親水部にスルホ基を有するアニオン性界面活性剤や、長鎖アルキル鎖を有し親水部にカルボキシル基を有するアニオン性界面活性剤などを用いる。具体的には、炭素鎖長がＣ８、Ｃ１０、Ｃ１２、Ｃ１４、Ｃ１６のアニオン性界面活性剤を用いることが好ましい。炭素鎖長がＣ１２の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（ＳＤＳ）が挙げられる。 Examples of the anionic surfactant to be dissolved in ion-exchanged water include an anionic surfactant having a long alkyl chain and a sulfo group in the hydrophilic portion, and an anion having a long alkyl chain and a carboxyl group in the hydrophilic portion. A surfactant is used. Specifically, it is preferable to use an anionic surfactant having a carbon chain length of C8, C10, C12, C14, or C16. An example of an anionic surfactant having a carbon chain length of C12 is sodium dodecyl sulfate (SDS).
なお、アニオン性界面活性剤の他にカチオン性界面活性剤をイオン交換水に溶解させてもよい。この場合、多層構造を形成するためにはアニオン性界面活性剤はカチオン性界面活性剤と比べて相対的に多くする必要があるが、割合としては９：１とすることも可能であるし、６：４とすることも可能である。カチオン性界面活性剤を加えることによって、酸化亜鉛結晶の角が丸くなり、発がん性を抑制することが可能になる。 In addition to the anionic surfactant, a cationic surfactant may be dissolved in the ion exchange water. In this case, in order to form a multilayer structure, the anionic surfactant needs to be relatively larger than the cationic surfactant, but the ratio can be 9: 1. 6: 4 is also possible. By adding a cationic surfactant, the corners of the zinc oxide crystal are rounded, and carcinogenicity can be suppressed.
カチオン性界面活性剤としては、長鎖アルキル鎖を有する四級アンモニウム塩型カチオン性界面活性剤などを用いる。例えばセチルトリメチルアンモニウムブロミド（ＣＴＡＢ）を用いることが可能である。 As the cationic surfactant, a quaternary ammonium salt type cationic surfactant having a long alkyl chain is used. For example, cetyltrimethylammonium bromide (CTAB) can be used.
水溶液はアルカリ性であれば足りるが、酸化亜鉛結晶の形状を板状に近い形状とするために、ｐＨは１０〜１４の範囲とすることが好ましい。なお、以下の実施例１、２で示すように、ｐＨを１２．０〜１２．５とした場合は、酸化亜鉛結晶は六角板状の構造となり、ｐＨを１３．０〜１３．８とした場合は、花弁状構造となる。ｐＨ調整剤としては、種々のものが考えられるが、例えばアンモニア水溶液を用いることが可能である。 The aqueous solution need only be alkaline, but the pH is preferably in the range of 10 to 14 in order to make the shape of the zinc oxide crystals close to a plate shape. As shown in Examples 1 and 2 below, when the pH was 12.0 to 12.5, the zinc oxide crystals had a hexagonal plate structure, and the pH was 13.0 to 13.8. In the case, it becomes a petal-like structure. Various pH adjusting agents are conceivable. For example, an aqueous ammonia solution can be used.
撹拌後の混合溶液をろ過・洗浄する方法としては、濾過器を用いたり、遠心分離を行った後にイオン交換水で外溶液の洗浄を行ったりすることが考えられる。また、合わせて超音波照射を行うことも可能である。 As a method for filtering and washing the mixed solution after stirring, it is conceivable to use a filter or to wash the outer solution with ion-exchanged water after centrifugation. In addition, ultrasonic irradiation can be performed together.
得られた結晶を乾燥させる際は、温度は１００℃〜１５０℃程度で数分〜数時間程度行うことが好ましい。なお、結晶性を高めるために、得られた酸化亜鉛結晶を粉砕して、焼成することも可能である。この場合、温度は２００℃〜８００℃程度とし、数分〜数時間程度行うことが好ましい。 When drying the obtained crystal | crystallization, it is preferable to carry out temperature for about several minutes-about several hours at about 100 to 150 degreeC. In addition, in order to improve crystallinity, the obtained zinc oxide crystal can be pulverized and fired. In this case, the temperature is preferably about 200 ° C. to 800 ° C., and is preferably performed for about several minutes to several hours.
図２は、アニオン性界面活性剤を含む水溶液に亜鉛イオンを加えることでアニオン性界面活性剤層と酸化亜鉛層とからなる多層構造が形成される様子を示した図である。この図に示すように、アニオン性界面活性剤の疎水基部は互いに向き合ってつながり、疎水性のアニオン性界面活性剤層（アニオン性界面活性剤の分子集合体）を形成している。また、亜鉛イオン（Ｚｎ２＋）は静電的相互作用によってアニオン性界面活性剤の親水基部周辺に酸化亜鉛層を形成している。アニオン性界面活性剤層と酸化亜鉛層は互いに重なり合うことによって多層構造を形成する。多層構造は数ナノメートル程度の周期性を有する構造（ラメラ構造）になっている。 FIG. 2 is a diagram showing a state in which a multilayer structure composed of an anionic surfactant layer and a zinc oxide layer is formed by adding zinc ions to an aqueous solution containing an anionic surfactant. As shown in this figure, the hydrophobic groups of the anionic surfactant are connected to each other to form a hydrophobic anionic surfactant layer (molecular assembly of anionic surfactant). Zinc ions (Zn 2+ ) form a zinc oxide layer around the hydrophilic base of the anionic surfactant by electrostatic interaction. The anionic surfactant layer and the zinc oxide layer overlap each other to form a multilayer structure. The multilayer structure is a structure having a periodicity of about several nanometers (lamella structure).
また、上記疎水性のアニオン性界面活性剤層は、略規則的なメソ構造を有する。当該アニオン性界面活性剤層には、ヒアルロン酸などの肌の保湿成分やアラントインなどの創傷治療成分を内包させることが可能である。よって、これらの成分を有する酸化亜鉛結晶を生成する際には、予め水溶液中に肌の保湿成分や創傷治療成分を加えておく。 The hydrophobic anionic surfactant layer has a substantially regular mesostructure. The anionic surfactant layer can contain a skin moisturizing component such as hyaluronic acid and a wound treatment component such as allantoin. Therefore, when producing zinc oxide crystals having these components, a skin moisturizing component and a wound healing component are added in advance to the aqueous solution.
<効果>
本発明の生成方法により生成される酸化亜鉛結晶は、マイクロスケールの板状の構造を有するため、球状粒子などに比べて紫外線などの光を吸収する実効面積が大きくなり、優れたサンスクリーン剤などの材料として用いることが可能になる。同時に、アニオン性界面活性剤と酸化亜鉛層とからなるナノスケールの多層構造に肌の保湿成分や創傷治療成分を内包させることができるため、皮膚の保湿性を一定に保つことが可能な新規なサンスクリーン剤や切り傷などの回復を促進する新規な創傷治療剤などの材料として用いることが可能になる。
<Effect>
Since the zinc oxide crystal produced by the production method of the present invention has a microscale plate-like structure, the effective area for absorbing light such as ultraviolet rays is larger than that of spherical particles and the like, and an excellent sunscreen agent, etc. It becomes possible to use it as a material. At the same time, a nano-scale multilayer structure consisting of an anionic surfactant and a zinc oxide layer can contain skin moisturizing ingredients and wound healing ingredients, making it possible to keep skin moisturizing constant. It can be used as a material such as a novel wound healing agent that promotes recovery of sunscreen agents and cuts.
<酸化亜鉛結晶の生成方法>
本実施例の酸化亜鉛結晶を生成するために、アニオン性界面活性剤としてドデシル硫酸ナトリウム（ＳＤＳ）を用い、酸化亜鉛の出発原料として硫酸亜鉛七水和物（ＺｎＳＯ４・７Ｈ２Ｏ）を用い、ｐＨ調整剤としてアンモニア水（ＮＨ３（ａｑ））を用いた。
<Method of forming zinc oxide crystals>
In order to produce the zinc oxide crystals of this example, sodium dodecyl sulfate (SDS) was used as the anionic surfactant, and zinc sulfate heptahydrate (ZnSO 4 .7H 2 O) was used as the starting material for zinc oxide. Ammonia water (NH 3 (aq)) was used as a pH adjuster.
図３は、本実施例の酸化亜鉛結晶の生成方法の流れを示す。まずステップＳ０３０１において、所定量のドデシル硫酸ナトリウムをイオン交換水に溶解させ、０ｍＭ（ドデシル硫酸ナトリウム不添加）、１００ｍＭ、３００ｍＭ、５００ｍＭのドデシル硫酸ナトリウム水溶液４５ｍｌをそれぞれ生成した。次にステップＳ０３０２において、ステップＳ０３０１にて得られた各硫酸ナトリウム水溶液にアンモニア水５ｍｌを加えて数分間撹拌し、ｐＨ１２．０〜１２．５に調整した。次にステップＳ０３０３において、ステップＳ０３０２にて得られた各溶液に２Ｍの硫酸亜鉛七水和物を１０ｍｌ加えて２４時間撹拌した。次にステップＳ０３０４において、ステップＳ０３０３にて得られた各溶液に対して超音波照射を１０分間行った後、遠心分離を行ってイオン交換水で外溶液の洗浄を行った。次にステップＳ０３０５において、ステップＳ０３０４にて得られた粒子を１２０℃で１２時間乾燥処理を行った。 FIG. 3 shows the flow of the method for producing zinc oxide crystals of this example. First, in step S0301, a predetermined amount of sodium dodecyl sulfate was dissolved in ion-exchanged water to produce 45 ml of 0 mM (no sodium dodecyl sulfate added), 100 mM, 300 mM, and 500 mM sodium dodecyl sulfate aqueous solutions. Next, in step S0302, 5 ml of aqueous ammonia was added to each sodium sulfate aqueous solution obtained in step S0301, and the mixture was stirred for several minutes to adjust the pH to 12.0 to 12.5. Next, in Step S0303, 10 ml of 2M zinc sulfate heptahydrate was added to each solution obtained in Step S0302, and stirred for 24 hours. Next, in step S0304, each solution obtained in step S0303 was subjected to ultrasonic irradiation for 10 minutes, and then centrifuged to wash the outer solution with ion-exchanged water. Next, in step S0305, the particles obtained in step S0304 were dried at 120 ° C. for 12 hours.
<解析方法>
上記生成方法により得られた試料について構造特性評価を行った。具体的には、得られた試料についてＸ線解析測定を行い、走査型電子顕微鏡（ＳＥＭ）及び透過型電子顕微鏡（ＴＥＭ）により観察した。
<Analysis method>
The structural characteristics of the sample obtained by the above generation method were evaluated. Specifically, the obtained sample was subjected to X-ray analysis measurement and observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM).
<結果>
図４は、走査型電子顕微鏡（ＳＥＭ）により得られた酸化亜鉛結晶の像である（左図：０ｍＭドデシル硫酸ナトリウムを用いた場合、右図：５００ｍＭドデシル硫酸ナトリウムを用いた場合）。この像が示すように、上記ステップＳ０３０１において５００ｍＭのドデシル硫酸ナトリウムを生成した場合は、直径約２〜７μｍ、厚さ４００〜５００ｎｍの六角板状結晶が確認された。また、ステップＳ０３０１において、ドデシル硫酸ナトリウムを添加しなかった場合は、形成される酸化亜鉛結晶の実効面積（板面積）は小さくなった。
<Result>
FIG. 4 is an image of a zinc oxide crystal obtained by a scanning electron microscope (SEM) (left figure: when 0 mM sodium dodecyl sulfate is used, right figure: when 500 mM sodium dodecyl sulfate is used). As shown in this image, when 500 mM sodium dodecyl sulfate was produced in step S0301, hexagonal plate crystals having a diameter of about 2 to 7 μm and a thickness of 400 to 500 nm were confirmed. Moreover, in step S0301, when sodium dodecyl sulfate was not added, the effective area (plate area) of the zinc oxide crystal formed became small.
図５は、Ｘ線解析測定により得られた酸化亜鉛結晶の低角ＸＲＤパターンを示す図である（横軸：２θ（ＣｕＫα）、縦軸：Ｘ線強度）。この図に示すように、ステップＳ０３０１において、１００ｍＭ、３００ｍＭ、５００ｍＭのドデシル硫酸ナトリウム水溶液を用いた場合は、２θ＝２．９°、５．８°、８．６°近傍に、ラメラ構造の（１００）、（２００）、（３００）面に帰属する回折ピークが検出された。一方、ドデシル硫酸ナトリウムを加えなかった場合は、これらの回折ピークは検出されなかった。 FIG. 5 is a diagram showing a low-angle XRD pattern of a zinc oxide crystal obtained by X-ray analysis measurement (horizontal axis: 2θ (CuKα), vertical axis: X-ray intensity). As shown in this figure, in the case where 100 mM, 300 mM, and 500 mM sodium dodecyl sulfate aqueous solution was used in step S0301, the lamellar structure (2θ = 2.9 °, 5.8 °, 8.6 °) Diffraction peaks attributed to the (100), (200), and (300) planes were detected. On the other hand, when no sodium dodecyl sulfate was added, these diffraction peaks were not detected.
また、図６は、透過型電子顕微鏡（ＴＥＭ）により得られた六角板状結晶の像である（左図中央の黒い部分が六角板状粒子）。この像が示すように、六角板状粒子の外縁部分に層状の構造が形成されており、当該多層構造の周期はナノスケールとなっている。 FIG. 6 is an image of a hexagonal plate crystal obtained by a transmission electron microscope (TEM) (the black part in the center of the left diagram is a hexagonal plate particle). As this image shows, a layered structure is formed at the outer edge portion of the hexagonal plate-like particles, and the period of the multilayer structure is nanoscale.
<考察>
以上の結果から、上記生成方法により生成される酸化亜鉛結晶は、全体としてマイクロスケールの六角板状のモルフォロジーを有し、一部にナノスケールのアニオン性界面活性剤層と酸化亜鉛層とからなる多層構造（ラメラ構造）を有していることがわかる。
<Discussion>
From the above results, the zinc oxide crystal produced by the production method has a microscale hexagonal plate-like morphology as a whole, and is partially composed of a nanoscale anionic surfactant layer and a zinc oxide layer. It turns out that it has a multilayer structure (lamella structure).
上記酸化亜鉛結晶は六角板状のモルフォロジーを有しているため、針状形状の結晶や球状の結晶と比較して、紫外線などの光を吸収する実効面積が大きい。また、ナノスケールの多層構造を有しているため、ヒアルロン酸などの皮膚の保湿性を保つ成分やアラントインなどの創傷治療成分を内包させることが可能になる。 Since the zinc oxide crystal has a hexagonal plate-like morphology, the effective area for absorbing light such as ultraviolet rays is larger than that of a needle-like crystal or a spherical crystal. Moreover, since it has a nanoscale multilayer structure, it becomes possible to encapsulate components for maintaining the moisture of the skin such as hyaluronic acid and wound treatment components such as allantoin.
よって、紫外線吸収効率が高く、かつ皮膚の保湿性を一定に保つことが可能な新規なサンスクリーン剤や、切り傷などの回復を促進する新規な創傷治療剤などの材料として用いることができる。 Therefore, it can be used as a material such as a novel sunscreen agent that has high ultraviolet absorption efficiency and can keep the moisture retention of the skin constant, and a novel wound treatment agent that promotes recovery of cuts and the like.
<酸化亜鉛結晶の生成方法・解析方法>
基本的に実施例１の酸化亜鉛結晶の生成方法の流れと同じであるが、ステップＳ０３０２において混合溶液をｐＨ１３．０〜１３．８に調整して酸化亜鉛結晶を生成・抽出した。また、得られた酸化亜鉛結晶を走査型電子顕微鏡により観察した。
<Methods for generating and analyzing zinc oxide crystals>
Basically, the flow of the method for producing zinc oxide crystals in Example 1 was the same, but in step S0302, the mixed solution was adjusted to pH 13.0 to 13.8 to produce and extract zinc oxide crystals. The obtained zinc oxide crystals were observed with a scanning electron microscope.
<結果>
図７は、走査型電子顕微鏡（ＳＥＭ）により得られた像である。この図が示すように、上記ステップＳ０３０１において５００ｍＭのドデシル硫酸ナトリウムを生成し、ステップＳ０３０２において混合溶液をｐＨ１３．０〜１３．８に調整した場合は、直径約２〜７μｍ、厚さ４００〜５００ｎｍの花弁状構造の酸化亜鉛結晶が確認された。なお、ステップＳ０３０２において、ドデシル硫酸ナトリウムを添加しなかった場合（０ｍＭのドデシル硫酸ナトリウム水溶液）は、酸化亜鉛結晶は形成されなかった。
<Result>
FIG. 7 is an image obtained by a scanning electron microscope (SEM). As shown in this figure, when 500 mM sodium dodecyl sulfate was produced in step S0301, and the mixed solution was adjusted to pH 13.0 to 13.8 in step S0302, the diameter was about 2 to 7 μm and the thickness was 400 to 500 nm. The petal-like structure of zinc oxide crystals was confirmed. In Step S0302, when no sodium dodecyl sulfate was added (0 mM sodium dodecyl sulfate aqueous solution), zinc oxide crystals were not formed.
<考察>
上記生成方法により生成される花弁状構造の酸化亜鉛結晶は、実施例１で得られた六角板状粒子と同様に板状構造になっている。なお、本実施例において示していないが、当該花弁状構造の酸化亜鉛結晶に関しても実施例１と同様にアニオン性界面活性剤層と酸化亜鉛層とからなる多層構造が存在する。
<Discussion>
The petal-like zinc oxide crystals produced by the production method have a plate-like structure similar to the hexagonal plate-like particles obtained in Example 1. Although not shown in this example, the petal-like zinc oxide crystal also has a multilayer structure composed of an anionic surfactant layer and a zinc oxide layer as in Example 1.
よって、本実施例にて生成される花弁状構造の酸化亜鉛結晶は、実施例１の六角板状の酸化亜鉛結晶と同様に、針状形状の結晶や球状の結晶と比較して紫外線などの光を吸収する実効面積が大きい。また、ナノスケールの多層構造を有しているため、ヒアルロン酸などの皮膚の保湿性を保つ成分やアラントインなどの創傷治療成分を内包させることが可能になる。 Therefore, the petal-like structure zinc oxide crystal produced in this example is similar to the hexagonal plate-like zinc oxide crystal of Example 1 in comparison with needle-like crystals and spherical crystals. Large effective area for absorbing light. Moreover, since it has a nanoscale multilayer structure, it becomes possible to encapsulate components for maintaining the moisture of the skin such as hyaluronic acid and wound treatment components such as allantoin.
Claims (8)
前記水溶液中に肌の保湿成分又は／及び創傷治療成分をさらに加えることで前記アニオン性界面活性剤層と酸化亜鉛層とからなる多層構造のアニオン性界面活性剤層に肌の保湿成分又は／及び創傷治療成分を含ませる酸化亜鉛結晶の生成方法。 A method for producing a zinc oxide crystal, wherein zinc oxide is added to an aqueous solution containing an anionic surfactant to produce a zinc oxide crystal having a multilayer structure composed of an anionic surfactant layer and a zinc oxide layer ,
By further adding a skin moisturizing component or / and a wound healing component to the aqueous solution, the skin moisturizing component or / and / or the multilayered anionic surfactant layer comprising the anionic surfactant layer and the zinc oxide layer. A method for producing zinc oxide crystals containing a wound healing component .
前記水溶液中に肌の保湿成分又は／及び創傷治療成分をさらに加えることで前記アニオン性界面活性剤層と酸化亜鉛層とからなる多層構造のアニオン性界面活性剤層に肌の保湿成分又は／及び創傷治療成分を含ませる酸化亜鉛結晶の生成方法。 A method for producing zinc oxide crystals, wherein zinc ions are added to an aqueous solution containing an anionic surfactant to produce plate-like zinc oxide crystals ,
By further adding a skin moisturizing component or / and a wound healing component to the aqueous solution, the skin moisturizing component or / and / or the multilayered anionic surfactant layer comprising the anionic surfactant layer and the zinc oxide layer. A method for producing zinc oxide crystals containing a wound healing component .
前記水溶液中に肌の保湿成分又は／及び創傷治療成分をさらに加えることで前記アニオン性界面活性剤層と酸化亜鉛層とからなる多層構造のアニオン性界面活性剤層に肌の保湿成分又は／及び創傷治療成分を含ませる酸化亜鉛結晶の生成方法。 A zinc oxide crystal production method in which zinc ions are added to an aqueous solution containing a relatively large amount of an anionic surfactant and a relatively small amount of a cationic surfactant. There,
By further adding a skin moisturizing component or / and a wound healing component to the aqueous solution, the skin moisturizing component or / and / or the multilayered anionic surfactant layer comprising the anionic surfactant layer and the zinc oxide layer. A method for producing zinc oxide crystals containing a wound healing component .
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| JP2013245139A (en) * | 2012-05-28 | 2013-12-09 | Chiba Inst Of Technology | Method for producing zinc oxide crystal |
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| JPH0648742A (en) * | 1992-07-27 | 1994-02-22 | Nitto Chem Ind Co Ltd | Interlaminar compound |
| JP4051433B2 (en) * | 2002-09-04 | 2008-02-27 | 独立行政法人産業技術総合研究所 | Zinc oxide polycrystalline tube |
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