JP7468993B2 - Composition for inhibiting adhesion of fine particles - Google Patents
Composition for inhibiting adhesion of fine particles Download PDFInfo
- Publication number
- JP7468993B2 JP7468993B2 JP2019037463A JP2019037463A JP7468993B2 JP 7468993 B2 JP7468993 B2 JP 7468993B2 JP 2019037463 A JP2019037463 A JP 2019037463A JP 2019037463 A JP2019037463 A JP 2019037463A JP 7468993 B2 JP7468993 B2 JP 7468993B2
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- Prior art keywords
- extract
- organic compound
- composition
- clay mineral
- skin
- Prior art date
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Images
Description
本発明は、化粧料に関し、特に微小粒子による肌ダメージを予防することができる化粧料に関する。 The present invention relates to cosmetics, and in particular to cosmetics that can prevent skin damage caused by microparticles.
大気中には、種々の化学物質や生体異物が浮遊・飛翔していることが知られている。具体的には、自動車、火力発電所、焼却炉、暖炉、タバコなどの排煙、火山噴火による噴出物、土壌粒子などが由来の粒子状物質(PM)、花粉、粉塵、硫黄酸化物(二酸化硫黄など)、窒素酸化物(二酸化窒素など)などの排出ガス、石綿など、マイクロスケールの粒子が存在する。 It is known that various chemical substances and xenobiotics float or fly in the air. Specifically, there are micro-scale particles such as particulate matter (PM) derived from smoke from automobiles, thermal power plants, incinerators, fireplaces, and cigarettes, ejecta from volcanic eruptions, and soil particles, pollen, dust, exhaust gases such as sulfur oxides (such as sulfur dioxide) and nitrogen oxides (such as nitrogen dioxide), and asbestos.
これらの微小粒子は、大気汚染を引き起こし、口や鼻から吸入することによって呼吸器系に悪影響を及ぼす他に、生体の最外層であり常に外界に曝されている皮膚からも体内に取り込まれ、肌にトラブルやダメージを生じさせることが懸念されている。例えば、タバコの排煙は窒素酸化物あるいは活性酸素種の生成を介して、皮膚におけるしわの形成や透明度を低下させることが知られているし、ある種の有機化合物は皮膚炎症を生じさせる危険性があり、また、粉塵の微小粒子がその表面に芳香族系炭化水素を吸着したまま皮膚組織を透過して遺伝子に影響することも指摘されている。また、スギやヒノキ等の花粉はアレルギー性鼻炎(花粉症)の原因となる。 These microparticles cause air pollution and have a negative effect on the respiratory system when inhaled through the mouth and nose. They can also be taken into the body through the skin, which is the outermost layer of the body and is constantly exposed to the outside world, and there are concerns that they can cause skin problems and damage. For example, cigarette smoke is known to cause wrinkles and reduce skin transparency through the production of nitrogen oxides or active oxygen species, and certain organic compounds can cause skin inflammation. It has also been pointed out that microparticles of dust can affect genes by penetrating skin tissue with aromatic hydrocarbons adsorbed to their surface. Pollen from cedars, cypresses, and other trees can also cause allergic rhinitis (hay fever).
そのため、微小粒子が皮膚に付着したり、皮膚を介して体内に入り込んだりして、悪影響を及ぼすのを防ぐための試みが検討されている。例えば、特許文献1には、αゲル構造を有する組成物を適用して皮膚表面に膜を形成することにより、微小汚染物質が肌に付着し透過するのを抑制することが記載されている。特許文献2には、両性及びアニオン性ポリマー含有組成物を皮膚や衣類の表面に適用することにより花粉の付着を防止することが記載されている。非特許文献1には、ホスホリルコリンとアクリル酸モノマーとを重合して得た導電性の被膜を形成する素材を、微小粒子の付着抑制用素材とすることが記載されている。
Therefore, attempts to prevent microparticles from adhering to the skin or penetrating the body through the skin and causing adverse effects are being considered. For example,
ところで、化粧料においては、ベントナイト等の粘土鉱物を有機化合物で修飾して得た有機変性粘土鉱物が、系の分散安定性やレオロジー調整性を高める素材として汎用されている(特許文献3)。 Incidentally, in cosmetics, organically modified clay minerals obtained by modifying clay minerals such as bentonite with organic compounds are widely used as materials that improve the dispersion stability and rheology control of the system (Patent Document 3).
特許文献1~2及び非特許文献1の素材では、微小粒子の皮膚への付着抑制が必ずしも
満足なものではなく、改善の余地があった。特に、非特許文献1のポリマー系素材では、肌に塗布した時の被膜の感触が不快感を与える場合があった。
かかる状況に鑑み、本発明は、微小粒子の皮膚表面への付着を抑制する技術を提供することを課題とする。
The materials of
In view of the above circumstances, an object of the present invention is to provide a technique for suppressing adhesion of microparticles to the skin surface.
本発明者らは、粘土鉱物からなる粉体が皮膚上に均一に並ぶこと、及び該粉体が通常負に荷電していることに着目し、該粉体を正電荷を有する有機化合物で修飾することにより、皮膚上で導電性の被膜を形成しうる複合体が得られることを見出した。そして、かかる導電性の被膜が、微小粒子の付着の抑制に優れることに想到し、本発明を完成させた。 The inventors noticed that clay mineral powder is uniformly arranged on the skin and that the powder is usually negatively charged, and discovered that by modifying the powder with a positively charged organic compound, a complex capable of forming a conductive coating on the skin can be obtained. They then came up with the idea that such a conductive coating is excellent at inhibiting the adhesion of microparticles, and thus completed the present invention.
すなわち、本発明は以下の通りである。
[1]有機化合物で修飾された粘土鉱物を含有する、微小粒子付着抑制用の組成物であって、前記有機化合物の分子サイズが前記粘土鉱物の電荷間距離の150%以下である、組成物。
[2]前記有機化合物の前記粘土鉱物に対する理論修飾率が50%以上である、[1]に記載の組成物。
[3]前記有機化合物がカチオン性又は両性化合物である、[1]又は[2]に記載の組成物。
[4]前記有機化合物がレシチンである、[3]に記載の組成物。
[5]前記粘土鉱物がベントナイト及びヘクトライトからなる群から選択される、[1]~[4]のいずれかに記載の組成物。
[6]皮膚外用剤である、[5]に記載の組成物。
[7]化粧料である、[6]に記載の組成物。
That is, the present invention is as follows.
[1] A composition for inhibiting adhesion of fine particles, comprising a clay mineral modified with an organic compound, wherein the molecular size of the organic compound is 150% or less of the inter-charge distance of the clay mineral.
[2] The composition described in [1], wherein the theoretical modification rate of the organic compound with respect to the clay mineral is 50% or more.
[3] The composition according to [1] or [2], wherein the organic compound is a cationic or amphoteric compound.
[4] The composition described in [3], wherein the organic compound is lecithin.
[5] The composition according to any one of [1] to [4], wherein the clay mineral is selected from the group consisting of bentonite and hectorite.
[6] The composition described in [5], which is a topical skin preparation.
[7] The composition according to [6], which is a cosmetic.
本発明によれば、微小粒子の皮膚への付着抑制作用に優れた組成物が提供される。かかる組成物は化粧料などの皮膚外用剤として好適に用い得る。また、本発明の組成物は、分散性にも優れ、オイルゲルや乳化剤型等の態様が好ましい。 The present invention provides a composition that has excellent properties for inhibiting adhesion of microparticles to the skin. Such a composition can be suitably used as a skin topical agent such as a cosmetic. The composition of the present invention also has excellent dispersibility, and is preferably in the form of an oil gel or emulsion.
本発明の組成物は、有機化合物で修飾された粘土鉱物(以降、本発明の複合体とも記す)を含有する。 The composition of the present invention contains a clay mineral modified with an organic compound (hereinafter also referred to as the complex of the present invention).
本発明の複合体における粘土鉱物は、通常は板状粉体である。板状であることにより、皮膚等に塗布したときに平面上に均一に並びやすくなる。後述するように本発明の組成物は電気的に中性に近い導電膜を形成できる。通常、電荷を帯びている微小粒子は、皮膚上での静電気により付着しやすいところ、皮膚上に塗布された本発明の組成物の膜が皮膚の帯電を抑制できるため、微小粒子の付着を抑制することができる。このように電荷を逃がしやすくするため、粘土鉱物は平面上に並ぶことが好ましい。 The clay mineral in the complex of the present invention is usually a plate-like powder. Being plate-like makes it easier for the clay mineral to be uniformly arranged on a flat surface when applied to the skin, etc. As described below, the composition of the present invention can form a conductive film that is nearly electrically neutral. Normally, charged microparticles tend to adhere to the skin due to static electricity, but the film of the composition of the present invention applied to the skin can suppress the charge on the skin, thereby suppressing the adhesion of the microparticles. In this way, it is preferable for the clay mineral to be arranged on a flat surface in order to make it easier for the charge to escape.
粘土鉱物は、通常は電荷を帯びており、正電荷でも負電荷でも構わないが、負電荷を有するものが好ましい。
粘土鉱物としては、スクメタイト系のヘクトライト、ベントナイトやモントリロナイト、カオリナイト、イライト、マリーン粘土鉱物(海泥)、デザートローズ粘土鉱物、パスカライトなどが挙げられ、これらのうちベントナイト及びヘクトライトが特に好ましい。
なお、これらはいずれも負電荷を有する。
粘土鉱物の帯電部位は、等間隔に配置しており、板状粉体では板に並行な方向に規則的に並んでいる。通常その電荷間距離は特開2011-150037号公報に開示される方法で算出することができる。例えば、ベントナイトの主成分であるNa型モンモリロナイトのアニオンサイト間の距離は約1nmである。
粘土鉱物は、通常化粧料に配合され得る大きさのものを複合体調製に用いることができる。例えば、粘土鉱物は、原料として流通時に通常は凝集しているところ、かかる二次粒子の体積平均粒子径が、0.5~1000μmのものが好ましいが、特に限定されない。なお、粘土鉱物は一般的に、化粧料等の組成物に配合・分散する際に加温・攪拌等の処理を施され、通常は粒子径が小さくなる。例えば、25~80℃程度の加温と高せん断速度の攪拌により、体積平均粒子径が好ましくは5μm以下、3μm以下、より好ましくは1μm以下となり得る。ここで粒子径は、乾式粒度分布測定装置(例えば、ベックマンコルター社製、LS 13 320)を用いてレーザー回折散乱法により測定された値である。
Clay minerals usually carry an electric charge, which may be either positively or negatively charged, but are preferably negatively charged.
Examples of clay minerals include sucmetite-based hectorite, bentonite, montrealonite, kaolinite, illite, marine clay minerals (sea mud), desert rose clay minerals, and pascalite, and among these, bentonite and hectorite are particularly preferred.
Incidentally, each of these has a negative charge.
The charged sites of the clay mineral are arranged at equal intervals, and in plate-like powder, they are regularly arranged in a direction parallel to the plates. The distance between the charges can usually be calculated by the method disclosed in JP 2011-150037 A. For example, the distance between anion sites of Na-montmorillonite, which is the main component of bentonite, is about 1 nm.
Clay minerals of a size that can be normally incorporated into cosmetics can be used for the preparation of the complex. For example, clay minerals are usually aggregated when distributed as raw materials, and the volume average particle size of the secondary particles is preferably 0.5 to 1000 μm, but is not particularly limited thereto. In addition, clay minerals are generally subjected to treatments such as heating and stirring when incorporated and dispersed in compositions such as cosmetics, and the particle size is usually reduced. For example, by heating at about 25 to 80° C. and stirring at a high shear rate, the volume average particle size can be preferably 5 μm or less, 3 μm or less, and more preferably 1 μm or less. Here, the particle size is a value measured by a laser diffraction scattering method using a dry particle size distribution measuring device (e.g., LS 13 320 manufactured by Beckman Coulter, Inc.).
本発明の複合体における有機化合物は、通常は帯電している粘土鉱物を効率的に修飾するために、電荷を帯びており、正電荷でも負電荷でも構わないが、水中で正電荷を有するもの、より具体的にはカチオン性化合物又は両性化合物が好ましい。
すなわち、本発明の複合体を構成する粘土鉱物と有機化合物とは、負電荷を有する粘土鉱物とカチオン性有機化合物との組み合わせが好ましい。
The organic compound in the complex of the present invention is electrically charged in order to efficiently modify the clay mineral, which is usually charged. The organic compound may be positively or negatively charged, but is preferably one that has a positive charge in water, more specifically, a cationic compound or an amphoteric compound.
That is, the clay mineral and organic compound constituting the complex of the present invention are preferably a combination of a negatively charged clay mineral and a cationic organic compound.
本発明の複合体における有機化合物は、前記粘土鉱物の帯電部位を効率的に修飾するため、粘土鉱物の電荷間距離に収まりやすい大きさのものである。具体的には、分子サイズが前記粘土鉱物の電荷間距離の150%以下であり、好ましくは120%以下であり、より好ましくは100%以下であり、さらに好ましくは80%以下である有機化合物を用いる。かかる大きさの有機化合物を用いることにより、本発明の複合体の修飾化率は高いものとなり、その結果、後述の中性化率も高いものとなるため、微小粒子の付着抑制作用を発揮する。
本明細書において「分子サイズ」は、協和界面科学製自動表面張力計CBVP-Zを用いる表面張力測定により表面過剰濃度を算出し、その逆数である分子断面積の平方根をとった値である分子間距離の値を指すものとすることができる。また、単分子膜の表面膜圧を測定してπ-A曲線(表面圧-面積曲線)から算出した値であってもよい(椿信之ら、油化学、第41巻、第7号、551-557、(1992) 参照)。
The organic compound in the complex of the present invention is of a size that is easily accommodated within the charge distance of the clay mineral in order to efficiently modify the charged sites of the clay mineral. Specifically, an organic compound is used whose molecular size is 150% or less, preferably 120% or less, more preferably 100% or less, and even more preferably 80% or less of the charge distance of the clay mineral. By using an organic compound of such a size, the modification rate of the complex of the present invention is high, and as a result, the neutralization rate described below is also high, thereby exerting an adhesion suppressing effect on microparticles.
In this specification, the term "molecular size" refers to the intermolecular distance, which is the square root of the molecular cross-sectional area, which is the reciprocal of the surface excess concentration calculated by measuring the surface tension using an automatic surface tensiometer CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. Alternatively, the term may refer to a value calculated from the π-A curve (surface pressure-area curve) by measuring the surface film pressure of a monolayer (see Nobuyuki Tsubaki et al., Oil Chemistry, Vol. 41, No. 7, pp. 551-557, (1992)).
本発明の複合体における有機化合物は、天然由来のものでも合成物でも構わないが、好ましくは天然由来のものである。なお、天然由来とは、動植物、鉱物等から得られた物自体のほか、その化合物を人工的に製造したものも含まれる。
天然由来のものとしては、レシチンが好ましく挙げられる。ここで、レシチンには水添レシチン及び非水添レシチンが含まれ、本発明においては所定の分子サイズを満たす限りにおいていずれも好ましく用いることができる。なお、水添のレシチン(ジステアロイルホスファチジルコリン)の場合、その分子サイズは、0.71nmである。
The organic compound in the complex of the present invention may be either naturally occurring or synthetic, but is preferably naturally occurring. Note that "naturally occurring" includes not only substances obtained from animals, plants, minerals, etc., but also compounds artificially produced from the same.
A preferred example of a naturally occurring lecithin is lecithin. Here, lecithin includes hydrogenated lecithin and non-hydrogenated lecithin, and either can be preferably used in the present invention as long as it satisfies a predetermined molecular size. In the case of hydrogenated lecithin (distearoylphosphatidylcholine), the molecular size is 0.71 nm.
また、本発明の複合体における有機化合物としては、4級アミノ基を有する化合物が好ましく挙げられる。具体的には、ステアリルトリメチルアンモニウムクロリド、ジメチルジステアリルアンモニウムクロリド等が挙げられる。 Preferable examples of the organic compound in the complex of the present invention include compounds having a quaternary amino group. Specific examples include stearyl trimethyl ammonium chloride, dimethyl distearyl ammonium chloride, etc.
本発明の複合体における、有機化合物による粘土鉱物の修飾の態様は、イオン結合および共有結合を介するものが含まれる。
複合化は、修飾に用いる有機化合物がカチオン化するpH領域の水媒体中で、該有機化合物と粘土鉱物とを混合することにより行うことができる。例えば、有機化合物としてレシチンを用いる場合は、好ましくはpH6以下、より好ましくはpH3以下、さらに好ま
しくはpH2~3条件であり、かかるpH条件の水溶液中でカチオン化したレシチンが粘土鉱物に結合することにより複合体が形成される。
In the complex of the present invention, the mode of modification of the clay mineral with the organic compound includes via ionic bonds and covalent bonds.
The complexation can be carried out by mixing the organic compound used for modification with the clay mineral in an aqueous medium in a pH range in which the organic compound is cationized. For example, when lecithin is used as the organic compound, the pH is preferably 6 or less, more preferably 3 or less, and even more preferably 2 to 3. In an aqueous solution under such pH conditions, the cationized lecithin binds to the clay mineral to form a complex.
本発明の複合体における、有機化合物の粘土鉱物に対する理論修飾率は、好ましくは50%以上、より好ましくは70%以上、さらに好ましくは80%以上である。また、実測修飾率は、好ましくは40%以上、より好ましくは55%以上、さらに好ましくは70%以上である。
ここで、修飾率とは、複合化している有機化合物と粘土鉱物の単位格子平面あたりに存在する、有機化合物の有する電荷(通常はカチオン)のモル量を、粘土鉱物の交換可能な電荷(通常はアニオン)部位のモル量で除した値であり、有機化合物が粘土鉱物の結合部位(通常は電荷部位)に充填している率を表す。
理論修飾率は、有機化合物の分子サイズと粘土鉱物の電荷間距離とから、算出することができる。具体的には、粘土鉱物の表面をその電荷間距離の間隔の格子に見立てて、該格子の上に有機化合物の分子サイズを直径とする円を重ならないように最密充填した場合の、粘土鉱物の表面積に対する有機化合物分子の占有面積の割合として算出できる。また、理論修飾率は、特開2011-150037号公報に開示される方法でも算出することができる。
また、実測修飾率は、熱分析装置により複合体の加熱重量変化を測定し、酸化発熱分解による重量減少量を複合化していた有機化合物の量とみなし、これを用いて算出した修飾率とすることができる。
In the composite of the present invention, the theoretical modification rate of the organic compound to the clay mineral is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more, and the measured modification rate is preferably 40% or more, more preferably 55% or more, and even more preferably 70% or more.
Here, the modification rate is the molar amount of charge (usually cation) of the organic compound present per unit lattice plane of the complexed organic compound and clay mineral divided by the molar amount of exchangeable charge (usually anion) sites of the clay mineral, and represents the rate at which the organic compound fills the binding sites (usually charge sites) of the clay mineral.
The theoretical modification rate can be calculated from the molecular size of the organic compound and the charge distance of the clay mineral. Specifically, the surface of the clay mineral is considered to be a lattice with a spacing of the charge distance, and a circle with a diameter of the molecular size of the organic compound is closely packed on the lattice so as not to overlap. The theoretical modification rate can also be calculated by the method disclosed in JP 2011-150037 A.
In addition, the actual modification rate can be calculated by measuring the change in weight of the complex when heated using a thermal analyzer, and regarding the amount of weight loss due to exothermic oxidative decomposition as the amount of organic compound that had been complexed.
前述の通り本発明の複合体は、通常は互いに反対の電荷を有する有機化合物により粘土鉱物が修飾されたものであるため、電荷的に中性に近い。電荷が打ち消され合って、得られる複合体が電気的に中性になった程度を表す「中性化率」(100%に近いほど中性化の程度が大きい)は、前述の修飾率と同義であってよい。
また、本発明の複合体は、電荷的に中性に近く、具体的にはイースパートアナライザ(ホソカワミクロン、EST-G)で測定(印加電圧:100V、粒子カウント数:1000、室温25℃
±2℃、湿度30%±3%、窒素ガス圧:0.02MPa)したときの、複合体の粒子の帯電量の絶
対値が好ましくは1.5μC/g以下、より好ましくは1.0μC/g以下、さらに好ましくは0.7μC/g以下、さらに好ましくは0.5μC/g以下、特に好ましくは0.4μC/g以下である。
As described above, the composite of the present invention is generally a clay mineral modified with an organic compound having opposite charges, and is therefore close to neutral in charge. The "neutralization rate" (the closer to 100%, the greater the degree of neutralization) which represents the degree to which the charges are cancelled out and the composite obtained is electrically neutral may be synonymous with the modification rate described above.
In addition, the complex of the present invention is nearly neutral in charge, and specifically, when measured with an ESPERT analyzer (HOSOKAWA MICRON, EST-G) (applied voltage: 100 V, particle count: 1000, room temperature 25° C.),
±2°C, humidity 30%±3%, nitrogen gas pressure: 0.02 MPa), the absolute value of the charge amount of the composite particles is preferably 1.5 μC/g or less, more preferably 1.0 μC/g or less, even more preferably 0.7 μC/g or less, even more preferably 0.5 μC/g or less, and particularly preferably 0.4 μC/g or less.
本発明の組成物は、微小粒子の付着抑制作用を有する。
これは、本発明の複合体が形成する導電性の被膜が、通常帯電している微小粒子を電荷反発により避けるためである。なお、被膜による物理的な付着抑制作用をも同時に生じることは妨げられない。
The composition of the present invention has an effect of inhibiting adhesion of fine particles.
This is because the conductive coating formed by the composite of the present invention repels microparticles that are normally charged due to charge repulsion. However, this does not prevent the coating from simultaneously exerting a physical adhesion suppressing effect.
なお、本明細書において微小粒子とは、微小物質全般をいい、通常は肌に悪影響を与えうるものであり、具体的には特に限定されないが、自動車、火力発電所、焼却炉、暖炉、タバコなどの排煙、火山噴火による噴出物、土壌粒子などが由来の粒子状物質(PM)、花粉、粉塵、硫黄酸化物(二酸化硫黄など)、窒素酸化物(二酸化窒素など)などの排出ガス、石綿などの、化学物質や生体異物をいう。また、通常、マイクロスケールの粒子であり、例えば長径50μm以下のものである。また、粒子の形状は特に問わない。 In this specification, microparticles refer to microscopic substances in general, and are usually substances that can have adverse effects on the skin. Examples of such substances include, but are not limited to, particulate matter (PM) derived from automobiles, thermal power plants, incinerators, fireplaces, and cigarette smoke, volcanic eruptions, and soil particles, as well as pollen, dust, exhaust gases such as sulfur oxides (sulfur dioxide, etc.), nitrogen oxides (nitrogen dioxide, etc.), asbestos, and other chemical substances and foreign substances in the body. In addition, microparticles are usually microscale particles, with a major axis of, for example, 50 μm or less. The shape of the particles is not particularly important.
一般に、微小粒子は肌表面に物理的な刺激を与えたり、表皮に入り込んで炎症性因子の放出を促す刺激を生じさせたりすることが知られている。本発明の組成物は、微小粒子が肌に付着することを抑制できることから、微小粒子による炎症惹起を抑制しうるので、肌ダメージの予防のためにも好ましく用いることができる。ここで、「肌ダメージ」とは、肌が健康でないあらゆる状態をいい、例えば、表皮細胞が刺激を受けて炎症性因子の放出により炎症が生じた状態や、その結果シワや色素沈着等が生じた状態をいう。 In general, it is known that microparticles can cause physical irritation to the skin surface or can penetrate into the epidermis and cause irritation that promotes the release of inflammatory factors. The composition of the present invention can inhibit adhesion of microparticles to the skin, and therefore can inhibit inflammation caused by microparticles, and can be preferably used to prevent skin damage. Here, "skin damage" refers to any condition in which the skin is not healthy, such as a condition in which epidermal cells are stimulated and inflammation occurs due to the release of inflammatory factors, or a condition in which wrinkles, pigmentation, etc. occur as a result.
したがって、本発明の組成物は、皮膚外用剤の態様とすることが好ましく、化粧料の態様とすることがさらに好ましい。化粧料としては、スキンケア化粧料、メークアップ化粧料、ヘアケア化粧料等特に限定されない。 Therefore, the composition of the present invention is preferably in the form of an external skin preparation, and more preferably in the form of a cosmetic. The cosmetic may be, but is not limited to, a skin care cosmetic, a make-up cosmetic, or a hair care cosmetic.
本発明の組成物の剤型としては、乳化剤型、ローション、オイル剤型、ジェル剤型、オイルゲル剤型、スプレー剤型、シートマスク剤型等、特に限定されない。
本発明の複合体は、組成物に他の界面活性剤を配合せずとも優れた分散性をも発揮するため、乳化剤型やオイルゲル剤型がより好ましい。
The formulation of the composition of the present invention is not particularly limited and may be an emulsion, a lotion, an oil, a gel, an oil gel, a spray, a sheet mask, or the like.
The complex of the present invention exhibits excellent dispersibility even without blending other surfactants in the composition, and therefore is more preferably in the form of an emulsion or oil gel.
本発明の組成物における、本発明の複合体の含有量は、組成物全量に対して総量で、好ましくは0.1質量%以上、より好ましくは1質量%以上、さらに好ましくは2質量%以上であり、また好ましくは20質量%以下、より好ましくは10質量%以下、さらに好ましくは5質量%以下である。例えば、本発明の複合体を油中水乳化剤型の組成物に配合する場合、組成物全量に対して、好ましくは0.5~5.0質量%、より好ましくは1.0~4.0質量%、さらに好ましくは2.0~3.5質量%の含有量とすることが好ましい。
かかる範囲とすることにより、所望の効果を得やすく、また処方設計の自由度を確保できる。
The content of the complex of the present invention in the composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, based on the total amount of the composition. For example, when the complex of the present invention is incorporated into a water-in-oil emulsion type composition, the content is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 4.0% by mass, even more preferably 2.0 to 3.5% by mass, based on the total amount of the composition.
By setting the content within this range, it is easy to obtain the desired effect and the freedom in formulation design can be ensured.
本発明の組成物においては、通常の皮膚外用剤等で使用される任意成分を、本発明の効果を損なわない限りにおいて任意に含有することができる。この様な任意成分としては、各種有効成分、油性成分、他の界面活性剤、多価アルコール、増粘剤、粉体類、紫外線吸収剤等が挙げられる。 The composition of the present invention may contain any optional ingredients used in ordinary skin preparations, etc., as long as they do not impair the effects of the present invention. Such optional ingredients include various active ingredients, oily ingredients, other surfactants, polyhydric alcohols, thickeners, powders, ultraviolet absorbers, etc.
有効成分としては、美白成分、シワ改善成分、抗炎症成分、他の動植物由来の抽出物等が挙げられる。
美白成分としては、一般的に化粧料に用いられているものであれば特に限定はない。例えば、4-n-ブチルレゾルシノール、アスコルビン酸グルコシド、3-О-エチルアスコルビン酸、アルブチン、エラグ酸、コウジ酸、リノール酸、ニコチン酸アミド、5,5'-ジプロピルビフェニル-2,2'-ジオール、5'-アデニル酸二ナトリウム、4-メ
トキシサリチル酸カリウム塩、ハイドロキノン、パントテン酸等が挙げられる。
The active ingredients include whitening ingredients, anti-wrinkle ingredients, anti-inflammatory ingredients, and extracts derived from other animals and plants.
The whitening ingredient is not particularly limited as long as it is one that is generally used in cosmetics, and examples thereof include 4-n-butylresorcinol, ascorbic acid glucoside, 3-O-ethyl ascorbic acid, arbutin, ellagic acid, kojic acid, linoleic acid, nicotinamide, 5,5'-dipropylbiphenyl-2,2'-diol, 5'-adenylic acid disodium, 4-methoxysalicylic acid potassium salt, hydroquinone, pantothenic acid, etc.
シワ改善成分としては、一般的に化粧料に用いられているものであれば特に限定はない。例えば、三フッ化イソプロピルオキソプロピルアミノカルボニルピロリジンカルボニルメチルプロピルアミノカルボニルベンゾイルアミノ酢酸ナトリウム、ニコチン酸アミド、ビタミンA又はその誘導体(レチノール、レチナール、レチノイン酸、トレチノイン、イソトレチノイン、レチノイン酸トコフェロール、パルミチン酸レチノール、酢酸レチノール等)、ウルソール酸ベンジルエステル、ウルソール酸リン酸エステル、ベツリン酸ベンジルエステル、ベンジル酸リン酸エステルが挙げられる。 There are no particular limitations on the wrinkle-improving ingredient, so long as it is one that is generally used in cosmetics. Examples include sodium trifluoride isopropyl oxopropyl aminocarbonyl pyrrolidine carbonyl methyl propyl aminocarbonyl benzoyl aminoacetate, nicotinamide, vitamin A or its derivatives (retinol, retinal, retinoic acid, tretinoin, isotretinoin, tocopherol retinoate, retinol palmitate, retinol acetate, etc.), ursolic acid benzyl ester, ursolic acid phosphate, benzylic acid benzyl ester, and benzilic acid phosphate.
抗炎症成分としては、グリチルリチン酸、グリチルレチン酸、アラントイン、イソプロピルメチルフェノール、クラリノン、グラブリジン、サリチル酸、トコフェロール酢酸エステル、トコフェロールニコチン酸エステル、ニコチン酸アミド、パントテン酸、パントテニルアルコール、及びこれらの塩又は誘導体等が挙げられ、好ましくは、グリチルリチン酸及びその塩、グリチルレチン酸及びその塩、パントテニルアルコール並びにパントテン酸及びその塩である。 Anti-inflammatory ingredients include glycyrrhizic acid, glycyrrhetinic acid, allantoin, isopropylmethylphenol, clarinone, glabridin, salicylic acid, tocopherol acetate, tocopherol nicotinate, nicotinamide, pantothenic acid, pantothenyl alcohol, and salts or derivatives thereof, with glycyrrhizic acid and its salts, glycyrrhetinic acid and its salts, pantothenyl alcohol, and pantothenic acid and its salts being preferred.
他の動植物由来の抽出物としては、一般的に化粧料等に用いられているものであれば特に限定はない。例えば、アケビエキス、アスナロエキス、アスパラガスエキス、アボカド
エキス、アマチャエキス、アーモンドエキス、アルニカエキス、アロエエキス、アロニアエキス、アンズエキス、イチョウエキス、インドキノエキス、ウイキョウエキス、ウドエキス、エイジツエキス、エゾウコギエキス、エンメイソウエキス、オウゴンエキス、オウバクエキス、オウレンエキス、オタネニンジンエキス、オトギリソウエキス、オドリコソウエキス、オレンジエキス、カキョクエキス、カッコンエキス、カモミラエキス、カロットエキス、カワラヨモギエキス、キウイエキス、キューカンバーエキス、グアバエキス、クジンエキス、クチナシエキス、クマザサエキス、クララエキス、クルミエキス、グレープフルーツエキス、黒米エキス、クロレラエキス、クワエキス、ケイケットウエキス、ゲットウヨウエキス、ゲンチアナエキス、ゲンノショウコエキス、紅茶エキス、ゴボウエキス、コメエキス、コメ発酵エキス、コメヌカ発酵エキス、コメ胚芽油、コケモモエキス、サルビアエキス、サボンソウエキス、ササエキス、サンシャエキス、サンショウエキス、シイタケエキス、ジオウエキス、シコンエキス、シソエキス、シナノキエキス、シモツケソウエキス、シャクヤクエキス、ショウキョウエキス、ショウブ根エキス、シラカバエキス、スギナエキス、ステビアエキス、ステビア発酵物、セイヨウキズタエキス、セイヨウサンザシエキス、セイヨウニワトコエキス、セイヨウノコギリソウエキス、セイヨウハッカエキス、セージエキス、ゼニアオイエキス、センキュウエキス、センブリエキス、ソウハクヒエキス、ダイオウエキス、ダイズエキス、タイソウエキス、タイムエキス、タンポポエキス、茶エキス、チョウジエキス、チンピエキス、甜茶エキス、トウガラシエキス、トウキエキス、トウキンセンカエキス、トウニンエキス、トウヒエキス、ドクダミエキス、トマトエキス、納豆エキス、ニンジンエキス、ニンニクエキス、ノバラエキス、ハイビスカスエキス、バクモンドウエキス、ハスエキス、パセリエキス、バーチエキス、ハマメリスエキス、ヒキオコシエキス、ヒノキエキス、ビワエキス、フキタンポポエキス、フキノトウエキス、ブクリョウエキス、ブッチャーブルームエキス、ブドウエキス、ブドウ種子エキス、ヘチマエキス、ベニバナエキス、ペパーミントエキス、ボダイジュエキス、ボタンエキス、ホップエキス、マツエキス、マヨナラエキス、マロニエエキス、ミズバショウエキス、ムクロジエキス、メリッサエキス、モズクエキス、モモエキス、ヤグルマギクエキス、ユーカリエキス、ユキノシタエキス、ユズエキス、ユリエキス、ヨクイニンエキス、ヨモギエキス、ラベンダーエキス、緑茶エキス、リンゴエキス、ルイボス茶エキス、レイシエキス、レタスエキス、レモンエキス、レンギョウエキス、レンゲソウエキス、ローズエキス、ローズマリーエキス、ローマカミツレエキス、ローヤルゼリーエキス、ワレモコウエキス等のエキスが好ましいものとして挙げられる。
The extracts derived from other animals and plants are not particularly limited as long as they are generally used in cosmetics and the like. For example, akebia extract, asparagus extract, avocado extract, amacha extract, almond extract, arnica extract, aloe extract, aronia extract, apricot extract, ginkgo extract, indian kinoko extract, fennel extract, udo extract, eizu extract, enmeiso extract, scutellaria root extract, phellodendron bark extract, coptis japonica extract, ginseng extract, hypericum extract, white lamb's foot extract, orange extract, kakyoku extract, pueraria root extract, chamomile extract, carrot extract, artemisia capillaris extract, kiwi extract, cucumber extract, guava extract, sophora root extract, gardenia extract, kumazasa extract, sophora flavescens extract, walnut extract, grapefruit ... Root extract, black rice extract, chlorella extract, mulberry extract, ginseng extract, alpinia gracilis extract, gentiana extract, geranium extract, black tea extract, burdock extract, rice extract, fermented rice extract, fermented rice bran extract, rice germ oil, cowberry extract, salvia extract, soapwort extract, bamboo extract, sanshou extract, zanthoxylum extract, shiitake mushroom extract, rehmannia root extract, lithospermum extract, perilla extract, linden extract, meadowsweet extract, peony extract, ginger extract, calamus root extract, birch extract, horsetail extract, stevia extract, fermented stevia, ivy extract, hawthorn extract, elderberry extract, yarrow extract, Mint extract, sage extract, mallow extract, cnidium extract, swertia bristlecone extract, soybean extract, tsinga extract, thyme extract, dandelion extract, tea extract, clove extract, tangerine extract, sweet tea extract, chili pepper extract, angelica extract, calendula extract, peach kernel extract, spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic extract, wild rose extract, hibiscus extract, burdock root extract, lotus extract, parsley extract, birch extract, witch hazel extract, sedge extract, cypress extract, loquat extract, coltsfoot extract, butterbur bud extract, bupleurum extract, butcher's broom extract, grape Examples of preferred extracts include grape seed extract, loofah extract, safflower extract, peppermint extract, linden extract, peony extract, hop extract, pine extract, mayonnaise extract, horse chestnut extract, skunk cabbage extract, soapberry extract, melissa extract, mozuku extract, peach extract, cornflower extract, eucalyptus extract, saxifrage extract, yuzu extract, lily extract, coix seed extract, mugwort extract, lavender extract, green tea extract, apple extract, rooibos tea extract, lychee extract, lettuce extract, lemon extract, forsythia extract, astragalus extract, rose extract, rosemary extract, Roman chamomile extract, royal jelly extract, and burnet extract.
油性成分としては、極性油、揮発性炭化水素油等が挙げられる。
極性油としては、合成エステル油として、ミリスチン酸イソプロピル、オクタン酸セチル、ミリスチン酸オクチルドデシル、パルミチン酸イソプロピル、ステアリン酸ブチル、ラウリン酸ヘキシル、ミリスチン酸ミリスチル、オレイン酸デシル、ジメチルオクタン酸ヘキシルデシル、乳酸セチル、乳酸ミリスチル、酢酸ラノリン、イソノナン酸2-エチルヘキシル、ステアリン酸イソセチル、イソステアリン酸イソセチル、12-ヒドロキシステアリン酸コレステリル、ジ-2-エチルヘキサン酸エチレングリコール、ジペンタエリスリトール脂肪酸エステル、モノイソステアリン酸N-アルキルグリコール、ジカプリン酸ネオペンチルグリコール、リンゴ酸ジイソステアリル、ジ-2-ヘプチルウンデカン酸グリセリル、トリ-2-エチルヘキサン酸トリメチロールプロパン、トリイソステアリン酸トリメチロールプロパン、テトラ-2-エチルヘキサン酸ペンタンエリスリトール、トリ-2-エチルヘキサン酸グリセリル、トリイソステアリン酸トリメチロールプロパンを挙げることができる。
The oily components include polar oils, volatile hydrocarbon oils, and the like.
Examples of polar oils include synthetic ester oils such as isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, 2-ethylhexyl isononanoate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, and ethyl di-2-ethylhexanoate. Examples of the fatty acid esters include ethylene glycol, dipentaerythritol fatty acid esters, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaneerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, and trimethylolpropane triisostearate.
さらに、セチル2-エチルヘキサノエート、2-エチルヘキシルパルミテート、トリミリスチン酸グリセリル、トリ-2-ヘプチルウンデカン酸グリセライド、ヒマシ油脂肪酸メチルエステル、オレイン酸オイル、セトステアリルアルコール、アセトグリセライド、パルミチン酸2-ヘプチルウンデシル、アジピン酸ジイソブチル、N-ラウロイル-L-
グルタミン酸-2-オクチルドデシルエステル、アジピン酸ジ-2-ヘプチルウンデシル、エチルラウレート、セバチン酸ジ-2-エチルヘキシル、ミリスチン酸2-ヘキシルデシル、パルミチン酸2-ヘキシルデシル、アジピン酸2-ヘキシルデシル、セバチン酸ジイソプロピル、コハク酸2-エチルヘキシル、酢酸エチル、酢酸ブチル、酢酸アミル、クエン酸トリエチル、オクチルメトキシシンナメート等も挙げられる。
In addition, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-
Other examples include 2-octyldodecyl glutamate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, and octyl methoxycinnamate.
また、天然油として、アボガド油、ツバキ油、タートル油、マカデミアナッツ油、トウモロコシ油、ミンク油、オリーブ油、ナタネ油、卵黄油、ゴマ油、パーシック油、小麦胚芽油、サザンカ油、ヒマシ油、アマニ油、サフラワー油、綿実油、エノ油、大豆油、落花生油、茶実油、カヤ油、コメヌカ油、シナギリ油、日本キリ油、ホホバ油、胚芽油、トリグリセリン、トリオクタン酸グリセリル、トリイソパルミチン酸グリセリル等が挙げられる。 Other natural oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, and glyceryl triisopalmitate.
揮発性炭化水素油としては、直鎖でも分岐鎖でもよい炭素数12~16のアルカン、具体的にはイソドデカン、イソヘキサデカン等が挙げられる。 Volatile hydrocarbon oils include alkanes having 12 to 16 carbon atoms, which may be linear or branched, such as isododecane and isohexadecane.
界面活性剤としては、脂肪酸セッケン(ラウリン酸ナトリウム、パルミチン酸ナトリウム等)、ラウリル硫酸カリウム、アルキル硫酸トリエタノールアミンエーテル等のアニオン界面活性剤類、塩化ステアリルトリメチルアンモニウム、塩化ベンザルコニウム、ラウリルアミンオキサイド等のカチオン界面活性剤類、ベタイン系界面活性剤(アルキルベタイン、アミドベタイン、スルホベタイン等)、イミダゾリン系両性界面活性剤(2-ココイル-2-イミダゾリニウムヒドロキサイド-1-カルボキシエチロキシ2ナトリウム塩等)、アシルメチルタウリン等の両性界面活性剤類、ソルビタン脂肪酸エステル類(ソルビタンモノステアレート、セスキオレイン酸ソルビタン等) 、グリセリン脂肪酸エステ
ル類(モノステアリン酸グリセリル等)、プロピレングリコール脂肪酸エステル類(モノステアリン酸プロピレングリコール等)、硬化ヒマシ油誘導体、グリセリンアルキルエーテル、POEソルビタン脂肪酸エステル類(POEソルビタンモノオレエート、モノステアリン酸ポリオキシエチレンソルビタン等)、POEソルビット脂肪酸エステル類(POE-ソルビットモノラウレート等)、POEグリセリン脂肪酸エステル類(POE-グリセリンモノイソステアレート等)、POE脂肪酸エステル類(ポリエチレングリコールモノオレート、POEジステアレート等)、POEアルキルエーテル類(POE2-オクチルドデシルエーテル等)、POEアルキルフェニルエーテル類(POEノニルフェニルエーテル等)、プルロニック(登録商標)型類、POE・POPアルキルエーテル類(POE・POP2-デシルテトラデシルエーテル等)、テトロニック類、POEヒマシ油・硬化ヒマシ油誘導体(POEヒマシ油、POE硬化ヒマシ油等)、ショ糖脂肪酸エステル、アルキルグルコシド等の非イオン界面活性剤類、等が挙げられる。
Examples of surfactants include anionic surfactants such as fatty acid soaps (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, and alkyl triethanolamine ether sulfate; cationic surfactants such as stearyl trimethylammonium chloride, benzalkonium chloride, and laurylamine oxide; betaine surfactants (alkyl betaines, amido betaines, sulfobetaines, etc.); imidazoline amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); and amphoteric surfactants such as acyl methyl taurine; sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.). , glycerin fatty acid esters (glyceryl monostearate, etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), hydrogenated castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbitan fatty acid esters (POE-sorbitan monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE fatty acid esters (polyoxyethylene sorbitan monolaurate, etc.), triethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE 2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonylphenyl ether, etc.), Pluronic (registered trademark) types, POE-POP alkyl ethers (POE-POP 2-decyltetradecyl ether, etc.), Tetronics, POE castor oil-hydrogenated castor oil derivatives (POE castor oil, POE hydrogenated castor oil, etc.), sucrose fatty acid esters, nonionic surfactants such as alkyl glucosides, etc.
多価アルコールとしては、ポリエチレングリコール、グリセリン、1,3-ブチレングリコール、エリスリトール、ソルビトール、キシリトール、マルチトール、プロピレングリコール、ジプロピレングリコール、ジグリセリン、イソプレングリコール、1,2-ペンタンジオール、2,4-ヘキシレングリコール、1,2-ヘキサンジオール、1,2-オクタンジオール等が挙げられる。 Examples of polyhydric alcohols include polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1,2-hexanediol, and 1,2-octanediol.
増粘剤としては、グアーガム、クインスシード、カラギーナン、ガラクタン、アラビアガム、ペクチン、マンナン、デンプン、キサンタンガム、カードラン、メチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルヒドロキシプロピルセルロース、コンドロイチン硫酸、デルマタン硫酸、グリコーゲン、ヘパラン硫酸、ヒアルロン酸、ヒアルロン酸ナトリウム、トラガントガム、ケラタン硫酸、コンドロイチン、ムコイチン硫酸、ヒドロキシエチルグアガム、カルボキシメチルグアガム、デキストラン、ケラト硫酸、ローカストビーンガム、サクシノグルカン、カロニン酸,キチン、キト
サン、カルボキシメチルキチン、寒天、ポリビニルアルコール、ポリビニルピロリドン、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー、ポリアクリル酸ナトリウム、ポリエチレングリコール、ベントナイト等が挙げられる。
Examples of thickening agents include guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, curdlan, methylcellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methylhydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, keratosulfuric acid, locust bean gum, succinoglucan, caronic acid, chitin, chitosan, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, sodium polyacrylate, polyethylene glycol, and bentonite.
粉体類としては、表面を処理されていてもよい、マイカ、タルク、カオリン、合成雲母、炭酸カルシウム、炭酸マグネシウム、無水ケイ酸(シリカ)、酸化アルミニウム、硫酸バリウム等の粉体類、表面を処理されていてもよい、ベンガラ、黄酸化鉄、黒酸化鉄、酸化コバルト、群青、紺青、酸化チタン、酸化亜鉛の無機顔料類、表面を処理されていてもよい、雲母チタン、魚燐箔、オキシ塩化ビスマス等のパール剤類、レーキ化されていてもよい赤色202号、赤色228号、赤色226号、黄色4号、青色404号、黄色5号、赤色505号、赤色230号、赤色223号、橙色201号、赤色213号、黄色204号、黄色203号、青色1号、緑色201号、紫色201号、赤色204号等の有機色素類、ポリエチレン末、ポリメタクリル酸メチル、ナイロン粉末、オルガノポリシロキサンエラストマー等の有機粉体類、が挙げられる。 Examples of powders include powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, and barium sulfate, which may be surface-treated; inorganic pigments such as red iron oxide, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, Prussian blue, titanium oxide, and zinc oxide, which may be surface-treated; pearlescent agents such as titanium mica, fish phosphorus foil, and bismuth oxychloride, which may be surface-treated; organic dyes such as Red No. 202, Red No. 228, Red No. 226, Yellow No. 4, Blue No. 404, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, and Red No. 204, which may be laked; and organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, and organopolysiloxane elastomer.
紫外線吸収剤としては、パラアミノ安息香酸系紫外線吸収剤、アントラニル酸系紫外線吸収剤、サリチル酸系紫外線吸収剤、桂皮酸系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、糖系紫外線吸収剤、2-(2'-ヒドロキシ-5'-t-オクチルフェニル)ベンゾ
トリアゾール、4-メトキシ-4'-t-ブチルジベンゾイルメタン等の紫外線吸収剤類
、等が挙げられる。
Examples of the ultraviolet absorber include para-aminobenzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, sugar-based ultraviolet absorbers, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 4-methoxy-4'-t-butyldibenzoylmethane, and other ultraviolet absorbers.
以下に、実施例を挙げて、本発明について更に詳細に説明を加えるが、本発明がかかる実施例にのみ限定されないことは言うまでもない。 The present invention will be described in more detail below with reference to examples, but it goes without saying that the present invention is not limited to these examples.
<試験例1>複合体の調製及び修飾率の検討
(1)カチオン領域の確認
修飾に用いる有機化合物においては、その水溶液においてカチオン化するpH領域をゼータ電位測定(大塚電子製ELSZ-2)により確認した。
<Test Example 1> Preparation of Complex and Examination of Modification Rate (1) Confirmation of Cationic Region The pH region in which the organic compound used for modification is cationized in its aqueous solution was confirmed by zeta potential measurement (ELSZ-2, manufactured by Otsuka Electronics Co., Ltd.).
(2)分子サイズの算出
前記有機化合物としては、レシチン(水添レシチンEmulmetik 950、Lucas Meyer Cosmetics製)、ジメチルジオクタデシルアンモニウムクロリド(富士フイルム和光純薬株式会社製)、及びラウリルベタイン(Amphitol 24B、花王株式会社製)を用いた。
ジメチルジオクタデシルアンモニウムクロリド及びラウリルベタインについては、表面張力測定(協和界面科学製自動表面張力計CBVP-Z)により、表面過剰濃度を算出した。表面過剰濃度の逆数である分子断面積から分子サイズを求めた。
レシチンの分子サイズは、単分子膜のπ-A曲線から算出された文献値((椿信之ら、油化学、第41巻、第7号、551-557、(1992))を採用した。
(2) Calculation of Molecular Size As the organic compounds, lecithin (hydrogenated lecithin Emulmetik 950, manufactured by Lucas Meyer Cosmetics), dimethyldioctadecylammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and lauryl betaine (Amphitol 24B, manufactured by Kao Corporation) were used.
For dimethyldioctadecylammonium chloride and lauryl betaine, the surface excess concentration was calculated by surface tension measurement (Kyowa Interface Science Co., Ltd., automatic surface tensiometer CBVP-Z). The molecular size was calculated from the molecular cross-sectional area, which is the reciprocal of the surface excess concentration.
The molecular size of lecithin was calculated from the π-A curve of a monolayer (Tsubaki, Nobuyuki et al., Oil Chemistry, Vol. 41, No. 7, pp. 551-557, (1992)).
(3)複合体の調製
各種有機化合物(終濃度1~25 mM)、ベントナイト(ホージュン、ベンゲルA)8 g、1N
HClまたはクエン酸を適量(pH調整用)、及び純水(up to 800g)を混合し、80±5℃
下で2時間、スターラー撹拌した。その後、pH2.5~3に調整したHCl水溶液にて洗浄し、遠心分離したのち、上清廃棄する洗浄操作を3回実施した。洗浄後、吸引ろ過した残渣を減
圧乾燥機(80℃、-0.1 MPa)にて一晩乾燥後、粉砕した。
(3) Preparation of complexes Various organic compounds (final concentration 1-25 mM), bentonite (Hojun, Bengel A) 8 g, 1N
Mix an appropriate amount of HCl or citric acid (for pH adjustment) and pure water (up to 800g) and heat at 80±5℃.
The mixture was stirred under a stirrer for 2 hours under agitation. After that, the mixture was washed with an aqueous HCl solution adjusted to pH 2.5-3, centrifuged, and the supernatant was discarded. This washing procedure was repeated three times. After washing, the residue was suction filtered and dried overnight in a vacuum dryer (80°C, -0.1 MPa) and then pulverized.
(4)修飾率の測定
熱分析装置(リガク製TP2-R/TG-DTA)により、加熱重量変化を測定し、酸化発熱分解による重量減少量を複合化した有機化合物量とし、中性化度を算出した。
測定条件:温度範囲20~500℃、昇温速度5℃/min.、大気雰囲気下
試料容器:アルミパン
修飾率は、複合化している有機化合物/ベントナイト(交換可能な電荷部位に換算)のmol比×100(%)とした
(4) Measurement of modification rate The change in weight upon heating was measured using a thermal analyzer (Rigaku TP2-R/TG-DTA), and the weight loss due to exothermic oxidative decomposition was regarded as the amount of complexed organic compounds, from which the degree of neutralization was calculated.
Measurement conditions: Temperature range 20-500°C, heating rate 5°C/min., in air Sample container: aluminum pan Modification rate was calculated as molar ratio of the composite organic compound/bentonite (converted into exchangeable charge sites) x 100 (%)
表1に、各有機化合物の分子サイズと修飾率を示す。
分子サイズが1.12 nmのジメチルジオクダデシルアンモニウムクロリドや1.78 nmのラウリルベタインでは、修飾率はそれぞれ46.4%、24.7%と低かった。一方、分子サイズが0.71
nmと小さいレシチンでは、92.3%と高い修飾率となりほぼ完全に中性化されたといえる。
Table 1 shows the molecular size and modification rate of each organic compound.
The modification rates of dimethyldioctadecylammonium chloride (1.12 nm) and lauryl betaine (1.78 nm) were low, at 46.4% and 24.7%, respectively.
In the case of small lecithin (nm), the modification rate was as high as 92.3%, which means that the molecule was almost completely neutralized.
<試験例2>付着抑制効果の検討
(1)試料 以下の粉体粒子を用いた。
実施例1:試験例1で調製したレシチン修飾ベントナイト複合体
実施例2:ジアルキルアンモニウム塩修飾ベントナイト「ベントン38V」(エレメンティスジャパン社製)
比較例1:ベントナイト
比較例2:ケラチンパウダー
Test Example 2: Study of adhesion suppression effect (1) Sample The following powder particles were used.
Example 1: Lecithin-modified bentonite complex prepared in Test Example 1 Example 2: Dialkylammonium salt-modified bentonite "Benton 38V" (manufactured by Elementis Japan Co., Ltd.)
Comparative Example 1: Bentonite Comparative Example 2: Keratin Powder
(2)粉体粒子(基剤)の帯電量の測定
実施例・比較例のいずれかの粉体粒子をガラス棒瓶に入れ3分間振とうし帯電前処理(強制帯電)とした。帯電している各粉体粒子の帯電量を、イースパートアナライザ(ホソカワミクロン、EST-G)を用いて測定した。測定条件は、印加電圧:100V、粒子カウント
数:1000、室温25℃±2℃、湿度30%±3%、窒素ガス圧:0.02MPaとした。
(2) Measurement of the charge amount of powder particles (base material) Either the powder particles of the Example or Comparative Example were placed in a glass rod bottle and shaken for 3 minutes as a pre-charging treatment (forced charging). The charge amount of each charged powder particle was measured using an Espart Analyzer (Hosokawa Micron, EST-G). The measurement conditions were as follows: applied voltage: 100V, particle count: 1000, room temperature 25°C ± 2°C, humidity 30% ± 3%, nitrogen gas pressure: 0.02MPa.
(3)花粉への帯電移行量の測定
花粉をガラス棒瓶に入れ3分間振とうし、帯電前処理(強制帯電)とした。
実施例・比較例のいずれかの粉体粒子の10質量%エタノール溶液を調製し、人工皮革(サプラーレ)に均一に塗布・乾燥した後、その人工皮革上に帯電している花粉を散布し、窒素ガスを吹き付け花粉を剥離した。遊離した花粉1000個の帯電量をイースパートアナライザを用いて測定した(測定条件は(2)と同様)。(剥離後の花粉の帯電量-散布前の花粉の帯電量)の絶対値を花粉への帯電移行量とした。
(3) Measurement of the amount of charge transferred to pollen Pollen was placed in a glass rod bottle and shaken for 3 minutes as a pre-charging treatment (forced charging).
A 10% by mass ethanol solution of the powder particles of either the Example or Comparative Example was prepared, uniformly applied to an artificial leather (Sapplar) and dried, and then charged pollen was sprinkled on the artificial leather and nitrogen gas was sprayed to peel off the pollen. The charge of 1,000 liberated pollen grains was measured using an e-spert analyzer (measurement conditions were the same as in (2)). The absolute value of (charge amount of pollen after peeling - charge amount of pollen before sprinkling) was taken as the charge transfer amount to the pollen.
結果を図1に示す。横軸は、粉体粒子(基剤)の帯電量であり、その絶対値が小さいほど中性化の程度が大きいことを示す。縦軸は、塗膜から花粉を剥離した時の、遊離した花粉への帯電移行量であり、大きいほど塗膜に付着した花粉が剥離されにくいことを示す。修飾化ベントナイト(実施例1及び2)の形成する塗膜では、花粉への帯電移行量が小さく、付着抑制効果が確認された。 The results are shown in Figure 1. The horizontal axis represents the amount of charge on the powder particles (base), and the smaller the absolute value, the greater the degree of neutralization. The vertical axis represents the amount of charge transferred to the free pollen when the pollen is peeled off from the coating, and the greater the value, the more difficult it is for the pollen adhering to the coating to be peeled off. In the coating formed by modified bentonite (Examples 1 and 2), the amount of charge transferred to the pollen was small, confirming the adhesion suppression effect.
Claims (6)
前記有機化合物の分子サイズが前記粘土鉱物の電荷間距離の150%以下であり、
前記有機化合物がレシチン及びジアルキルアンモニウム塩からなる群から選択され、
前記粘土鉱物がベントナイト及びヘクトライトからなる群から選択され、
前記有機化合物で修飾された粘土鉱物が形成する導電性の被膜が、皮膚の帯電を抑制することにより、前記微小粒子の付着が抑制される、組成物(ただし、フキタンポポ花エキスを含有する組成物、及びワサビノキ種子エキスを含有する組成物を除く)。 A composition for suppressing adhesion of fine particles, comprising a clay mineral modified with an organic compound,
The molecular size of the organic compound is 150% or less of the charge distance of the clay mineral;
the organic compound is selected from the group consisting of lecithin and dialkylammonium salts;
The clay mineral is selected from the group consisting of bentonite and hectorite;
A composition (excluding a composition containing coltsfoot flower extract and a composition containing horseradish seed extract) in which a conductive coating formed by the clay mineral modified with the organic compound suppresses the static electricity of the skin, thereby inhibiting the adhesion of the microparticles.
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