JP2010018578A - COSMETIC COMPOSITION CONTAINING POLY-gamma-L-GLUTAMIC ACID-CROSSLINKED MATERIAL - Google Patents
COSMETIC COMPOSITION CONTAINING POLY-gamma-L-GLUTAMIC ACID-CROSSLINKED MATERIAL Download PDFInfo
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- JP2010018578A JP2010018578A JP2008182309A JP2008182309A JP2010018578A JP 2010018578 A JP2010018578 A JP 2010018578A JP 2008182309 A JP2008182309 A JP 2008182309A JP 2008182309 A JP2008182309 A JP 2008182309A JP 2010018578 A JP2010018578 A JP 2010018578A
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Abstract
Description
本発明は、ポリ−γ−L−グルタミン酸架橋体を有効成分とする化粧品組成物に関するものであり、特に、化粧品、医薬部外品、医療用品、衛生用品、医薬品に利用されるものである。 The present invention relates to a cosmetic composition comprising a poly-γ-L-glutamic acid cross-linked product as an active ingredient, and is particularly used for cosmetics, quasi-drugs, medical products, hygiene products, and pharmaceuticals.
人の皮膚を覆っている角質層は、薄く柔軟で且つ体内の水分を保ち、健常な皮膚状態を維持するように調節している。乾燥した大気中においても水分を失うことなく生命活動を維持できるのは、外界と接しているこの角質層が存在しているからであることはよく知られている。 The stratum corneum covering the human skin is thin and flexible, and is adjusted so as to maintain moisture in the body and maintain a healthy skin state. It is well known that the existence of this stratum corneum in contact with the outside world can maintain life activity without losing moisture even in a dry atmosphere.
しかしながら、我々は環境要因等(例えば、温度変化、湿度変化、光、水との接触、洗剤の使用等)により、しばしば表皮に何らかの損傷をきたすことがある。ダメージを受けた皮膚は、硬く、弾力性も失われ、カサカサとした肌荒れ状態となる。こうした肌荒れ皮膚は、近年、急増傾向にあるアトピー性皮膚炎との関連性も指摘されており、深刻なスキントラブルを招く恐れもある。 However, we often cause some damage to the epidermis due to environmental factors (eg temperature change, humidity change, light, contact with water, use of detergents, etc.). Damaged skin is hard, loses elasticity, and becomes rough and rough. Such rough skin has recently been pointed out to be associated with atopic dermatitis, which is rapidly increasing, and may cause serious skin troubles.
日常生活における皮膚への悪影響のほとんどが、紫外線により発生する活性酸素、過酸化脂質に起因する物である。紫外線は、可視光線に近い、波長の長いほうから、A、B、Cに分けられる。C波は波長が約250nmと短く、エネルギーが大きく、皮膚癌の原因になるといわれているが、幸いなことに地表に届く前にほとんど吸収されている。A波(波長が約350nm)、B波(波長が約300nm)は、地表に届き、肌に酸化力として悪影響を与える。A波は皮膚の内部まで届き、シワの原因になるが、B波は皮膚の表面を焼き、一時的な軽いやけどをさせ、色黒を進行させる。 Most of the adverse effects on the skin in daily life are caused by active oxygen and lipid peroxide generated by ultraviolet rays. Ultraviolet light is divided into A, B, and C from the longer wavelength, which is close to visible light. The C-wave has a short wavelength of about 250 nm, has a large energy, and is said to cause skin cancer. Fortunately, it is almost absorbed before reaching the surface of the earth. A wave (wavelength is about 350 nm) and B wave (wavelength is about 300 nm) reach the earth's surface and adversely affect the skin as oxidizing power. The A wave reaches the inside of the skin and causes wrinkles, but the B wave burns the surface of the skin, causing a temporary light burn and a darkening of the color.
健康な肌は、外部の刺激から内部を守る自己防衛機能を持っている。しかし、近年の環境破壊から来る過度の刺激に対しては、自己防衛機能だけでは充分な防衛が出来ないのが現状である。外部刺激の主なものは紫外線による酸化反応である。紫外線による障害を防ぐためには、自己防衛機能を補足し、酸化チタン、酸化亜鉛等の紫外線反射(散乱)剤、ベンゾフェノン誘導体等の紫外線吸収剤などが有用である(特許文献1〜4参照)。しかし、これらの紫外線反射剤、紫外線吸収剤は、紫外線防御の持続性などの特性でなお不充分であり、また、いずれも敏感肌に悪影響を与える。特に、紫外線吸収剤は、紫外線を吸収する部分がベンゼン核であり、ベンゼン核は敏感肌の人にアレルギー症状を与える。 Healthy skin has a self-defense function that protects the inside from external stimuli. However, the current situation is that the self-defense function alone cannot provide sufficient defense against the excessive stimuli resulting from environmental destruction in recent years. The main external stimulus is an oxidation reaction by ultraviolet rays. In order to prevent damage due to ultraviolet rays, an ultraviolet reflecting (scattering) agent such as titanium oxide and zinc oxide, an ultraviolet absorber such as a benzophenone derivative, and the like are useful (see Patent Documents 1 to 4). However, these UV reflectors and UV absorbers are still insufficient in properties such as the durability of UV protection, and both have an adverse effect on sensitive skin. Particularly, in the ultraviolet absorber, the portion that absorbs ultraviolet rays is a benzene nucleus, and the benzene nucleus gives allergic symptoms to people with sensitive skin.
また、紫外線反射剤や紫外線吸収剤を配合した化粧品の場合には、その量にもよるが、安定性、におい、べたつきなどの問題が発生する。さらに、これらを多量に配合した場合には、塗布時に白浮きや、のびが悪くなるなどの使用感の問題が生じる。 In the case of cosmetics containing an ultraviolet reflector or ultraviolet absorber, problems such as stability, odor, and stickiness occur depending on the amount of cosmetics. Furthermore, when these are blended in a large amount, problems such as white floating at the time of application and a feeling of use such as poor spread occur.
一方、微生物が生産するバイオポリマーが有望視されており、その中でも、アミノ酸が縮重合して構成されるポリアミノ酸と呼ばれる一群のバイオポリマーの潜在能力に注目が集まっている。このポリアミノ酸としては、ポリ−γ−グルタミン酸(以下、「PGA」と表記することがある)、ポリ−ε−リジンおよびシアノファイシンの3種類がこれまでに同定されている。 On the other hand, biopolymers produced by microorganisms are promising, and among them, attention is focused on the potential of a group of biopolymers called polyamino acids composed of amino acids by condensation polymerization. Three types of polyamino acids have been identified so far: poly-γ-glutamic acid (hereinafter sometimes referred to as “PGA”), poly-ε-lysine and cyanophysin.
これらポリアミノ酸群の一つであるPGAは、グルタミン酸のα−アミノ基とγ−カルボキシル基とがアミド結合したポリアミノ酸であり、古くから日本人に親しまれている納豆の糸引きの主体物質として知られる。PGAの魅力的な機能としては、生分解性及び高吸水性を兼ね備えている点が知られており、これらの機能を利用して、上述した化粧料をはじめ、医療品、食品等、種々の分野、用途で用いられることが期待されている。 PGA, one of these polyamino acid groups, is a polyamino acid in which the α-amino group and γ-carboxyl group of glutamic acid are amide-bonded. known. As an attractive function of PGA, it is known that it has both biodegradability and high water absorption. By using these functions, various cosmetics, medical products, foods, and the like described above can be used. It is expected to be used in fields and applications.
すでに、種々の用途のPGAが製品化されているが、現在、製品化されているPGAは、D−グルタミン酸及びL−グルタミン酸が不規則に結合した化学的にヘテロなγ−DL−ポリグルタミン酸(以下、「DL−PGA」と表記することがある)である。さらに詳細に説明を行うと、現在製品化されているDL−PGAは、納豆菌やその類縁菌から生産されるもので、D−グルタミン酸及びL−グルタミン酸の配列、およびその含有比率は生産菌の培養毎に変動する。一般に、ポリアミノ酸の構造的特徴(構成するアミノ酸の光学活性や種類、分子サイズ、結合様式など)は、その機能に強く影響を与えることから、これらDL−PGAは、製造ロット毎にその性質が異なってしまい、所望の品質を有するDL−PGAを安定して製造することが困難である。 PGAs for various uses have already been commercialized. Currently, commercially available PGAs are chemically heterogeneous γ-DL-polyglutamic acids in which D-glutamic acid and L-glutamic acid are irregularly bound ( Hereinafter, it may be expressed as “DL-PGA”). In more detail, DL-PGA currently commercialized is produced from Bacillus natto and its related bacteria, and the sequences of D-glutamic acid and L-glutamic acid, and the content ratio thereof, It varies from culture to culture. In general, the structural characteristics of polyamino acids (optical activity and type of constituent amino acids, molecular size, binding mode, etc.) strongly influence their functions. Therefore, these DL-PGAs have different properties for each production lot. It is difficult to stably produce a DL-PGA having a desired quality.
一方、ホモポリ−γ−グルタミン酸を生産する菌も報告されている。例えば、炭疸菌Bacillus anthracisはD−グルタミン酸のみからなるポリ−γ−D−グルタミン酸(以下、D−PGAと記載することもある)を生産する事が報告されている(非特許文献1、非特許文献2、非特許文献3)。しかし、本菌は強い病原性を有する細菌であるため、工業的なPGA生産菌としては不適切であり、生産されるD−PGAの分子量も小さい。また、好アルカリ性細菌Bacillus haloduransは、L−グルタミン酸のみからなるポリ−γ−L−グルタミン酸(以下L−PGAと記載することもある)を生産する事も報告されている非特許文献3)。しかし、本菌の生産するL−PGAは分子量が極めて小さく、実用的な性能を得るには不十分である。 On the other hand, bacteria producing homopoly-γ-glutamic acid have also been reported. For example, Bacillus anthracis has been reported to produce poly-γ-D-glutamic acid (hereinafter sometimes referred to as D-PGA) consisting only of D-glutamic acid (Non-patent Document 1, Non-Patent Document 1, Patent Document 2, Non-Patent Document 3). However, since this bacterium is a bacterium having a strong pathogenicity, it is inappropriate as an industrial PGA-producing bacterium, and the molecular weight of D-PGA produced is small. In addition, it is reported that the alkalophilic bacterium Bacillus halodurans produces poly-γ-L-glutamic acid composed of only L-glutamic acid (hereinafter sometimes referred to as L-PGA) 3). However, L-PGA produced by this bacterium has an extremely small molecular weight, and is insufficient to obtain practical performance.
一方、高分子量のホモポリ−γ−グルタミン酸の生産菌として、好塩性古細菌Natrialba aegyptiacaが分子量10万〜100万程度のL−PGAを生産することが報告されている。しかし、本菌は液体培養条件下では分子量が10万程度と小さい、かつ殆どL−PGAを生産しないため、工業的な生産菌としては問題があった(非特許文献4、特許文献5)。 On the other hand, it has been reported that a halophilic archaeon, Naturalba aegyptica, produces L-PGA having a molecular weight of about 100,000 to 1,000,000 as a high-molecular-weight homopoly-γ-glutamic acid-producing bacterium. However, since this bacterium has a molecular weight as small as about 100,000 under liquid culture conditions and hardly produces L-PGA, there is a problem as an industrially produced bacterium (Non-patent Documents 4 and 5).
上記以外にも、L−PGAを生産する生物としては、ヒドラ等が挙げられるが、ヒドラの場合も同様に分子量が極めて小さいという問題がある。(非特許文献3) In addition to the above, examples of organisms that produce L-PGA include hydra and the like, but hydra also has a problem that its molecular weight is extremely small. (Non Patent Literature 3)
本発明者らは鋭意検討の結果、均一な光学純度でかつ高分子量のL−PGAを液体培養で大量に調製することを可能とした。より具体的には、数平均分子量が130万以上で、かつ均一な光学純度のL−PGAを、培養液1Lあたり4.99g以上の高い生産性で取得している(特許文献6)。 As a result of intensive studies, the present inventors have made it possible to prepare a large amount of L-PGA with uniform optical purity and high molecular weight by liquid culture. More specifically, L-PGA having a number average molecular weight of 1.3 million or more and uniform optical purity is obtained with a high productivity of 4.99 g or more per liter of culture solution (Patent Document 6).
また、L−PGAの架橋方法とL−PGA架橋体(特許文献7)、並びにL−PGA及びL−PGA架橋体のうち少なくとも一方を含むことを特徴とする皮膚外用剤(特許文献8)の報告がある。 Further, a method for cross-linking L-PGA, a cross-linked L-PGA (Patent Document 7), and an external preparation for skin (Patent Document 8) comprising at least one of L-PGA and L-PGA cross-linked body There is a report.
このような状況であるが、L−PGA架橋体を紫外線吸収剤と併用することにより、その紫外線吸収効果を損なわず皮膚に対する刺激性を低減できること及びのびがよくべたつき感を低減した化粧品は報告されていなかった。 Under such circumstances, there has been reported a cosmetic product that can reduce irritation to the skin without impairing its ultraviolet absorption effect and also has a good spread and reduced stickiness by using the L-PGA crosslinked product together with the ultraviolet absorber. It wasn't.
近年、オゾン層の破壊による紫外線量の増加や美白志向のニーズにより紫外線吸収化粧品が多く開発されている。しかし、紫外線吸収及び紫外線防御の持続性などの特性でなお不充分であり、また、いずれも敏感肌に悪影響を与える。特に、紫外線吸収剤は、紫外線を吸収する部分がベンゼン核であり、ベンゼン核は敏感肌の人にアレルギー症状を与える。また、紫外線反射剤や紫外線吸収剤を配合した化粧品の場合には、その量にもよるが、べたつきなどの問題が発生する。さらに、これらを多量に配合した場合には、塗布時に白浮きや、のびが悪くなるなどの使用感の問題が生じるため、皮膚への刺激性が低減されかつのびがよくべたつき感のない化粧品が望まれている。 In recent years, many UV-absorbing cosmetics have been developed due to the increase in the amount of ultraviolet rays due to the destruction of the ozone layer and the need for whitening. However, properties such as UV absorption and UV protection persistence are still insufficient and both adversely affect sensitive skin. Particularly, in the ultraviolet absorber, the portion that absorbs ultraviolet rays is a benzene nucleus, and the benzene nucleus gives allergic symptoms to people with sensitive skin. Further, in the case of a cosmetic containing an ultraviolet reflector or ultraviolet absorber, problems such as stickiness occur depending on the amount of the cosmetic. Furthermore, when these are blended in a large amount, problems such as white floatation and poor spread will occur at the time of application, so a cosmetic product with reduced irritation to the skin and good spread and no stickiness. It is desired.
本発明の目的は、上記問題を改善した、皮膚刺激性等の安全面に問題なく、さらにのびがよく、べたつき感のないL−PGA架橋体および/又はその塩と紫外線吸収剤を配合した化粧料及び皮膚外用剤を提供することにある。さらに、本発明の目的は、当該化粧料及び皮膚外用剤を含む化粧品、医薬部外品、医療用品、衛生用品、医薬品を提供することにある。 The object of the present invention is to improve the above-mentioned problems, have no safety problems such as skin irritation, and have a good spread and no stickiness, and a cosmetic composition containing an L-PGA crosslinked body and / or a salt thereof and an ultraviolet absorber. It is in providing a preparation and a skin external preparation. Furthermore, the objective of this invention is providing the cosmetics, a quasi-drug, a medical article, a hygiene article, and a pharmaceutical containing the said cosmetics and a skin external preparation.
本発明者らは、上記の目的を達成すべく鋭意努力した結果、L−PGA架橋体が有効であることを見出した。 As a result of diligent efforts to achieve the above object, the present inventors have found that an L-PGA crosslinked product is effective.
さらに、本発明者らは、紫外線吸収剤を含有する皮膚外用剤において、刺激の少ない皮膚外用剤を求めて鋭意研究努力を重ねた結果、紫外線吸収剤と共にL−PGA架橋体を用いることにより、紫外線吸収剤の皮膚への刺激性が低減され、かつのびがよくべたつき感を低減できることを見出し、本発明を完成させるに至った。 Furthermore, as a result of intensive research efforts for skin external preparations with less irritation in skin external preparations containing ultraviolet absorbers, the present inventors have used an L-PGA crosslinked product together with ultraviolet absorbents. It has been found that the irritation to the skin of the UV absorber is reduced, and that the feeling of stickiness can be reduced well and the present invention has been completed.
即ち、本発明は、以下の(1)〜(5)の発明を包含する。
(1)ポリ−γ−L−グルタミン酸架橋体と紫外線吸収剤を含有することを特徴とする化粧品組成物。
(2)紫外線吸収剤が、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、ケイ皮酸系紫外線吸収剤、トリアジン系紫外線吸収剤及びベンゾフェノン系紫外線吸収剤からなる群から選ばれた少なくとも1種の化合物であることを特徴とする1に記載の化粧品組成物。
(3)さらに、抗菌剤を含有することを特徴とする1又は2に記載の化粧品組
成物。
(4)抗菌剤が、有機系抗菌剤および/または無機系抗菌剤であることを特徴とする3に記載の化粧品組成物。
(5)化粧品、医薬部外品、医療用品、衛生用品または医薬品として利用されるものであることを特徴とする1〜4のいずれかに記載の化粧品組成物。
That is, the present invention includes the following inventions (1) to (5).
(1) A cosmetic composition comprising a crosslinked poly-γ-L-glutamic acid and an ultraviolet absorber.
(2) The group in which the UV absorber is composed of a benzoic acid UV absorber, an anthranilic acid UV absorber, a salicylic acid UV absorber, a cinnamic acid UV absorber, a triazine UV absorber, and a benzophenone UV absorber. 2. The cosmetic composition according to 1, wherein the cosmetic composition is at least one compound selected from the group consisting of:
(3) The cosmetic composition according to 1 or 2, further comprising an antibacterial agent.
(4) The cosmetic composition according to 3, wherein the antibacterial agent is an organic antibacterial agent and / or an inorganic antibacterial agent.
(5) The cosmetic composition according to any one of 1 to 4, which is used as a cosmetic, a quasi-drug, a medical product, a hygiene product, or a pharmaceutical product.
本発明のL−PGA架橋体と紫外線吸収剤を含有する化粧品組成物により、刺激が少なく、かつのび、しっとり感、かさつき難さを兼ね備えた化粧品、医薬部外品、医療用品、衛生用品、医薬品を提供することできる。特に、本発明によれば、抗菌剤を含有する皮膚外用剤において、刺激性の少ない皮膚外用剤を提供することができる。また、L−PGA架橋体は生物由来の天然高分子であるため安全性に優れており、本発明の化粧品組成物は長期にわたる使用に十分に耐えることができる。さらに、L−PGA架橋体は、L−PGAをγ線照射することにより得られるため大量生産が容易であり、その原料となるL−PGAは微生物から安価に製造できるため製造コストも安価となる。 The cosmetic composition containing the L-PGA cross-linked product of the present invention and an ultraviolet absorber has a low irritation and also has a soft, moist feeling, and difficult to hold, a quasi-drug, a medical product, a hygiene product, Can provide medicinal products. In particular, according to the present invention, a skin external preparation with less irritation can be provided in an external preparation for skin containing an antibacterial agent. Moreover, since L-PGA crosslinked body is a biologically derived natural polymer, it is excellent in safety, and the cosmetic composition of the present invention can sufficiently withstand long-term use. Furthermore, since the L-PGA cross-linked product can be obtained by irradiating L-PGA with γ-rays, mass production is easy, and L-PGA as a raw material can be produced at low cost from microorganisms, so that the production cost is also low. .
本発明の化粧品組成物は、L−PGA架橋体、並びに紫外線吸収剤を必須成分として含有する。 The cosmetic composition of the present invention contains an L-PGA crosslinked product and an ultraviolet absorber as essential components.
本発明の「L−PGA架橋体」とは、L−グルタミン酸のみからなるホモポリマ−であるL−PGAをγ線架橋したものである。L−PGAの構造は式(I)にて示される構造で、αCOOHの水素は水素であっても良いし他の金属対イオンでも良い。例えば、ナトリウム、カリウム、マグネシウム、マンガン、カルシウム、亜鉛及び鉄等一般的なものあれば限定する必要はない。そのなかでも好ましくはナトリウムである。 The “L-PGA cross-linked product” of the present invention is a product obtained by cross-linking L-PGA, which is a homopolymer consisting only of L-glutamic acid, by γ-rays. The structure of L-PGA is a structure represented by the formula (I), and the hydrogen of αCOOH may be hydrogen or another metal counter ion. For example, there is no need to limit the general materials such as sodium, potassium, magnesium, manganese, calcium, zinc and iron. Of these, sodium is preferred.
本発明の「分子量」とはプルラン標準物質の分子量換算にて算出した数平均分子量(Mn)のことを指す。 The “molecular weight” of the present invention refers to the number average molecular weight (Mn) calculated in terms of the molecular weight of the pullulan standard substance.
本発明のL−PGA架橋体は、既存の方法で得ることができる。たとえば、特許文献6(特開2007−314434号公報)に記載された方法で、L−PGAを得て、それを特許文献7(特開2008−120910号公報)に記載された方法によりγ線架橋して得ることができる。以下に、一例として、特許文献6および7を参考にしたL−PGA架橋体の製造方法を述べるがこれに限定されるものではない。 The L-PGA crosslinked product of the present invention can be obtained by an existing method. For example, L-PGA is obtained by the method described in Patent Document 6 (Japanese Patent Application Laid-Open No. 2007-314434), and γ-ray is obtained by the method described in Patent Document 7 (Japanese Patent Application Laid-Open No. 2008-120910). It can be obtained by crosslinking. Hereinafter, as an example, a method for producing an L-PGA crosslinked body with reference to Patent Documents 6 and 7 will be described, but the present invention is not limited thereto.
たとえば、独立行政法人産業技術総合研究所特許生物寄託センタ−に、ナトリアルバ エジプチアキア(Natrialba aegyptiaca)0830−82株(受託機関名:独立行政法人産業技術総合研究所特許生物寄託センタ−、 受託日:平成18年4月4日、受託番号:FERM BP−20872)、ナトリアルバ エジプチアキア(Natrialba aegyptiaca)0830−243株(受託機関名:独立行政法人産業技術総合研究所特許生物寄託センタ−、 受託日:平成18年4月4日、受託番号:FERM BP−20873)、またはナトリアルバ エジプチアキア(Natrialba aegyptiaca)0831−264株(受託機関名:独立行政法人産業技術総合研究所特許生物寄託センタ−、 受託日:平成18年4月4日、受託番号:FERM BP−20874)として寄託されている菌株をもちいてポリ−γ−L−グルタミン酸を得る場合、液体培養によりL−PGAを得ることができる。または、特許文献6(特開2007−314434号公報)に記載された方法で微生物を変異処理し、液体培養によりL−PGAを生産できる微生物を作製し、L−PGAを生産することもできる。また、ナトリアルバ エジプチアキア(Natrialba aegyptiaca)を常法により固相培養し、L−PGAを生産することもできる。 For example, the National Institute of Advanced Industrial Science and Technology (NIST) Patent Biological Depositary Center includes the Nationalba aegyptica 0830-82 strain (trusted organization: National Institute of Advanced Industrial Science and Technology Patent Biological Depositary). April 4, 2006, accession number: FERM BP-20872), Natrialba aegyptica 0830-243 strain (trusted organization name: National Institute of Advanced Industrial Science and Technology, Patent Biological Depositary Center), accession date: Heisei 18 April 4, 2000, accession number: FERM BP-20873), or Natrialba aegyptica 0831-264 strain (trusted organization name: National Institute of Advanced Industrial Science and Technology, Patent Organism Depositary) Deposit date: April 4, 2006, Deposit number: FERM BP-20874) When using the strain deposited to obtain poly-γ-L-glutamic acid, L-PGA can be obtained by liquid culture. . Alternatively, L-PGA can be produced by mutating a microorganism by the method described in Patent Document 6 (Japanese Patent Application Laid-Open No. 2007-314434), producing a microorganism capable of producing L-PGA by liquid culture, and producing L-PGA. Moreover, it is also possible to produce L-PGA by solid-phase culture of Natalba aegyptica by a conventional method.
液体培養する場合には、振とう培養、通気攪拌培養など好気条件などで行うことが望ましい。その際の培養温度は、30〜50℃、好ましくは35〜45℃が適当である。また、培地のpHは、水酸化ナトリウム、水酸化カリウム、アンモニア、塩酸、硫酸またそれらの水溶液などによって調整できるが、pH調整できれば限定されない。培養pH5.0−9.0、好ましくはpH6.0−8.5で培養するのが望ましい。また、培養期間は、通常2〜7日間程度でよい。また、培養時のNaCl濃度は10〜30%、好ましくは15〜25%で培養するのが望ましい。また、Yeast Extract濃度は0.1〜10%、好ましくは0.5〜5.0%濃度で培養するのが望ましい。また、固体培養の場合においても前期液体培養の場合と応用に、培養温度は30〜50℃、好ましくは35〜45℃、培養時のpHは5.0−9.0、好ましくはpH6.0−8.5、培養時のNaCl濃度は10−30%、好ましくは15〜25%、Yeast Extract濃度は0.1−10%、好ましくは0.5−5%濃度が採用される。このようにして培養すると、L−PGAは、主として菌体外に蓄積されて前記した培養物中に含まれる。特に限定はされないが、PGA生産液体培地−1(22.5% NaCl、2% MgSO4・7H2O、0.2% KCl、3% Trisodium Citrate、1% Yeast Extract、0.75% Casamino acid)を使用してもよく、各添加量は菌株にあわせて適宜調整すればよい。 In the case of liquid culture, it is desirable to carry out under aerobic conditions such as shaking culture and aeration stirring culture. The culture temperature at that time is 30 to 50 ° C, preferably 35 to 45 ° C. The pH of the medium can be adjusted with sodium hydroxide, potassium hydroxide, ammonia, hydrochloric acid, sulfuric acid, or an aqueous solution thereof, but is not limited as long as the pH can be adjusted. It is desirable to culture at a culture pH of 5.0 to 9.0, preferably at a pH of 6.0 to 8.5. In addition, the culture period is usually about 2 to 7 days. Further, it is desirable to culture at a NaCl concentration of 10 to 30%, preferably 15 to 25% during culture. Further, it is desirable to culture at a yeast extract concentration of 0.1 to 10%, preferably 0.5 to 5.0%. Also in the case of solid culture, the culture temperature is 30 to 50 ° C., preferably 35 to 45 ° C., and the pH during the culture is 5.0 to 9.0, preferably pH 6.0, in the case of liquid culture and application. -8.5, NaCl concentration during culture is 10-30%, preferably 15-25%, Yeast Extract concentration is 0.1-10%, preferably 0.5-5%. When cultured in this manner, L-PGA accumulates mainly outside the cells and is contained in the aforementioned culture. Although not specifically limited, PGA production liquid medium-1 (22.5% NaCl, 2% MgSO 4 .7H 2 O, 0.2% KCl, 3% Trisodium Citrate, 1% Yeast Extract, 0.75% Casamino acid ) May be used, and the amount of each additive may be appropriately adjusted according to the strain.
培養液中のL−PGAの定量方法としては、L−PGAを含む試料から、硫酸銅やエタノ−ルを用いて沈澱させ、その沈殿物の重量測定およびKijerder法による総窒素の測定を行なうもの(M.Bovarnick,J.Biol.Chem.,145巻、415ペ−ジ、1942年)、塩酸加水分解後のグルタミン酸量を測定する方法(R.D.Housewrigt,C.B.Thorne,J.Bacteriol.,60巻、89ペ−ジ、1950年)及び、塩基性色素との定量的な結合を利用した比色法(M.Bovarnick et al., J.Biol.Chem.,207巻、593ペ−ジ、1954年)が知られているが好ましくは、塩基性色素との定量的な結合を利用した比色法である。 As a method for quantifying L-PGA in a culture solution, precipitation is performed from a sample containing L-PGA using copper sulfate or ethanol, and the weight of the precipitate is measured and total nitrogen is measured by the Kijderder method. (M. Bovarnick, J. Biol. Chem., 145, 415, 1942), a method for measuring the amount of glutamic acid after hydrolysis of hydrochloric acid (RD Housewright, CB Thorne, J. Biol. Chem., 145, 415, 1942). Bacteriol., 60, 89, 1950) and a colorimetric method using quantitative binding with a basic dye (M. Bovarnick et al., J. Biol. Chem., 207, 593). Page, 1954) is known, but a colorimetric method utilizing quantitative binding with a basic dye is preferred.
塩基性色素としてはクリスタルバイオレット、アニリンブル−、サフラニンオ−、メチレンブル−、メチルバイオレット、トルイジネブル−、コンゴレッド、アゾカルマイン、チオニン、ヘマトキシリンなどがあげられるが、サフラニンオ−が好ましい。 Examples of basic dyes include crystal violet, aniline blue, safranino, methylene blue, methyl violet, toluine nebula, congo red, azocarmine, thionine, and hematoxylin, with safranino being preferred.
この培養物からL−PGAを分離、採取するには、硫酸銅やエタノ−ルを用いて沈澱させるなどの前記の公知の方法を用いればよい。一例を挙げると、例えば、培養液を遠心分離し、菌体を取り除く。続いて、得られた上清液に3倍量の水を加え希釈した後、pHを3.0に調整する。pH調整後、5時間 室温で攪拌した。その後、3倍量のエタノ−ルを加え、L−PGAを沈殿物として回収した。沈殿物を0.1mM Tris−HCl緩衝液(pH8.0)に溶解させ、低分子物質を透析により除去する。透析後、得られた液を核酸除去のため、DNase、RNase処理を行っても良いし、次いでタンパク質除去のために、Proteinase処理を行っても良い。Proteinase処理後、透析により低分子物質を除去しても良い。透析後、凍結乾燥等により、乾燥L−PGAを得ればよい。また、必要により陰イオン交換樹脂を用いた精製を行うことができるが、一般的な条件で精製可能である。 In order to separate and collect L-PGA from this culture, the above-mentioned known methods such as precipitation using copper sulfate or ethanol may be used. As an example, for example, the culture solution is centrifuged to remove the cells. Subsequently, after adding and diluting 3 times the amount of water to the obtained supernatant, the pH is adjusted to 3.0. After pH adjustment, the mixture was stirred at room temperature for 5 hours. Thereafter, 3 times the amount of ethanol was added, and L-PGA was recovered as a precipitate. The precipitate is dissolved in 0.1 mM Tris-HCl buffer (pH 8.0), and low-molecular substances are removed by dialysis. After dialysis, the resulting solution may be treated with DNase or RNase for nucleic acid removal, and then with proteinase treatment for protein removal. After the proteinase treatment, the low molecular weight substance may be removed by dialysis. After dialysis, dry L-PGA may be obtained by freeze drying or the like. Moreover, although refinement | purification using an anion exchange resin can be performed if necessary, it can refine | purify on general conditions.
本発明に使用するL−PGAの分子量は、特に限定されないが、好ましくは50万以上、より好ましくは80万以上、さらに好ましくは100万以上、特に好ましくは130万以上である。 Although the molecular weight of L-PGA used for this invention is not specifically limited, Preferably it is 500,000 or more, More preferably, it is 800,000 or more, More preferably, it is 1 million or more, Especially preferably, it is 1.3 million or more.
L−PGAの分子量の上限値は特に限定されるものではないが、前述のL−PGAの製造方法によれば、例えば、600万、最大で1500万のL−PGAを得ることができる。 The upper limit value of the molecular weight of L-PGA is not particularly limited, but according to the above-described L-PGA production method, for example, L-PGA having 6 million or 15 million at the maximum can be obtained.
このL−PGAは、古細菌によって生産されるために、納豆菌によって生産されるDL−PGAと比べて特有の臭気が軽減されるため、化粧品、医薬部外品、医療用品、衛生用品または医薬品の用途に利用しても品質を損なうことがない。 Since this L-PGA is produced by archaea and has a peculiar odor reduced compared to DL-PGA produced by Bacillus natto, cosmetics, quasi-drugs, medical products, hygiene products or pharmaceuticals The quality will not be impaired even if it is used for any purpose.
〔本発明に係るL−PGA架橋体の製造方法〕
本発明のL−PGA架橋体は、既存の方法で得ることができる。以下に、一例として、特開2008−120910号公報を参考にしたL−PGA架橋体の製造方法を述べるがこれに限定されるものではない。
[Method for producing L-PGA crosslinked product of the present invention]
The L-PGA crosslinked product of the present invention can be obtained by an existing method. Hereinafter, as an example, a method for producing an L-PGA crosslinked body with reference to JP-A-2008-120910 will be described, but the present invention is not limited thereto.
L−PGA架橋体の製造方法は、L−PGAの分子同士を架橋させる架橋工程を含んでいればよい。L−グルタミン酸のみからなる、光学活性が均一なL−PGAを原料として、これを架橋させることで、L−PGA架橋体の分子毎の性質が均一となる。よって、所望の品質を有するL−PGA架橋体を安定して製造することができる。 The manufacturing method of L-PGA crosslinked body should just include the bridge | crosslinking process which bridge | crosslinks the molecules of L-PGA. By cross-linking L-PGA consisting only of L-glutamic acid and having uniform optical activity as a raw material, the properties of the L-PGA cross-linked product are uniform. Therefore, it is possible to stably produce an L-PGA crosslinked product having a desired quality.
L−PGAは、溶媒に溶解させてL−PGAの溶液を作製した上で、架橋反応に供すればよい。L−PGAを溶解させる溶媒としては、L−PGAを溶解させることができる限り限定されるものではないが、例えば、水、アルコ−ル、アセトン、酢酸メチル、酢酸エチル等が挙げられ、中でも、水、メチルアルコ−ル、エチルアルコ−ルが好ましく、水がさらに好ましい。これらの溶媒に溶解させるときのL−PGAの濃度は、特に限定されるものではないが、好ましくは1重量%以上10重量%以下であり、さらに好ましくは2重量%以上8重量%以下であり、特に好ましくは2重量%以上7重量%以下である。また、L−PGAの溶液のpHは、特に限定されるものではないが、pH1.0以上14.0以下が好ましく、さらに好ましくはpH2.0以上13.0以下である。 L-PGA may be subjected to a crosslinking reaction after dissolving in a solvent to prepare a solution of L-PGA. The solvent for dissolving L-PGA is not limited as long as L-PGA can be dissolved, and examples thereof include water, alcohol, acetone, methyl acetate, and ethyl acetate. Water, methyl alcohol, and ethyl alcohol are preferable, and water is more preferable. The concentration of L-PGA when dissolved in these solvents is not particularly limited, but is preferably 1% by weight to 10% by weight, more preferably 2% by weight to 8% by weight. Particularly preferably, it is 2% by weight or more and 7% by weight or less. The pH of the L-PGA solution is not particularly limited, but is preferably pH 1.0 or higher and 14.0 or lower, more preferably pH 2.0 or higher and 13.0 or lower.
L−PGAの溶液に架橋反応を施すと、当該溶液中でL−PGAの架橋体が形成され、当該L−PGA架橋体が当該溶媒を含んで膨潤することで、ハイドロゲルが得られる。これは後述する本発明に係るハイドロゲルの態様の一つである。さらに、当該ハイドロゲルを凍結乾燥等することによって、溶媒成分を除去することによって、当該溶媒成分を含まないL−PGA架橋体を得ることができる。なお、本発明に係るハイドロゲルについては後述する。 When a cross-linking reaction is performed on the L-PGA solution, a cross-linked product of L-PGA is formed in the solution, and the L-PGA cross-linked product swells containing the solvent, whereby a hydrogel is obtained. This is one of the aspects of the hydrogel according to the present invention described later. Furthermore, L-PGA crosslinked body which does not contain the said solvent component can be obtained by removing the solvent component by freeze-drying the said hydrogel. The hydrogel according to the present invention will be described later.
上述のL−PGA架橋体の製造方法によれば、上述した架橋反応において、例えば、50%以上100%以下、特に70%以上100%以下のゲル化率でL−PGAを得ることができる。 According to the above-mentioned method for producing a crosslinked L-PGA, L-PGA can be obtained, for example, at a gelation rate of 50% to 100%, particularly 70% to 100% in the crosslinking reaction described above.
なお、本明細書において「ゲル化率」とは、原料として用いたL−PGAの重量に対する、架橋反応によって架橋体を形成したL−PGAの重量の百分率を意図する。換言すれば、「ゲル化率」とは、原料として用いたL−PGAに対して、得られるL−PGA架橋体ひいてはハイドロゲルの収率を表す。具体的には、架橋反応によって得たハイドロゲルの乾燥重量を、当該架橋反応に供したL−PGAの乾燥重量で割って得た数値に、百を乗じて算出する。 In the present specification, the “gelation rate” intends the percentage of the weight of L-PGA formed by a crosslinking reaction with respect to the weight of L-PGA used as a raw material. In other words, the “gelation rate” represents the yield of the obtained L-PGA crosslinked body and thus the hydrogel with respect to the L-PGA used as a raw material. Specifically, the value obtained by dividing the dry weight of the hydrogel obtained by the crosslinking reaction by the dry weight of L-PGA subjected to the crosslinking reaction is calculated by multiplying by 100.
L−PGAの架橋反応の方法は、L−PGAの分子同士を架橋させることができる限り限定されるものではなく、従来公知の方法で行なえばよい。例えば、架橋剤を用いてもよく、放射線を用いてもよいが、中でも放射線を用いることが好ましい。放射線を用いれば、架橋反応後に、架橋剤を除去する操作を必要とせず、高純度のL−PGA架橋体を製造することができる。 The method for the crosslinking reaction of L-PGA is not limited as long as L-PGA molecules can be crosslinked with each other, and may be performed by a conventionally known method. For example, a cross-linking agent may be used and radiation may be used, but it is preferable to use radiation. If radiation is used, an operation for removing the crosslinking agent is not required after the crosslinking reaction, and a highly pure L-PGA crosslinked product can be produced.
L−PGA架橋体の製造方法で使用可能な放射線としては、特に限定されるものではなく、α線、β線、γ線、電子線、中性子線、X線等を用いればよい。中でも、γ線が好ましい。γ線は、例えばコバルト60を線源とする照射装置等、従来公知の方法、機器を用いて発生させればよい。 The radiation that can be used in the method for producing an L-PGA crosslinked body is not particularly limited, and α rays, β rays, γ rays, electron beams, neutron rays, X rays, and the like may be used. Among these, γ rays are preferable. The γ rays may be generated using a conventionally known method and apparatus such as an irradiation apparatus using cobalt 60 as a radiation source.
また、L−PGAに照射する放射線の照射線量は、0.5kGy以上20kGy以下が好ましく、さらに好ましくは2kGy以上10kGy以下であり、特に好ましくは3kGy以上7kGy以下であるが、製造するL−PGA架橋体の用途等に応じて適宜設定すればよい。一般に照射線量が多ければ硬質のハイドロゲルを得ることができ、照射線量が少なければ軟質のハイドロゲルを得ることができる。例えば、照射線量を1kGy、3kGyとした場合、平板上に置いても自然に水平方向に広がる、流動性の高いハイドロゲルが得られ、照射線量が5kGy、7kGyでは、平板上に置いても水平方向に広がることなく静置可能な、流動性の低いハイドロゲルが得られる。 Further, the radiation dose to the L-PGA is preferably 0.5 kGy or more and 20 kGy or less, more preferably 2 kGy or more and 10 kGy or less, and particularly preferably 3 kGy or more and 7 kGy or less. What is necessary is just to set suitably according to the use etc. of a body. In general, a hard hydrogel can be obtained if the irradiation dose is large, and a soft hydrogel can be obtained if the irradiation dose is small. For example, when the irradiation dose is set to 1 kGy and 3 kGy, a highly fluid hydrogel that naturally spreads in the horizontal direction even when placed on a flat plate can be obtained. When the irradiation dose is 5 kGy or 7 kGy, the hydrogel is horizontal even when placed on a flat plate. A hydrogel with low fluidity that can be left stationary without spreading in the direction is obtained.
また、L−PGAの架橋に放射線を用いる場合、L−PGAの溶液を放射線透過性容器に入れて用いればよい。放射線透過性容器としては、特に限定されるものではなく、例えばガラス製バイアル瓶等、ガラス製容器等を用いることができる。 Moreover, when using a radiation for the bridge | crosslinking of L-PGA, what is necessary is just to put the solution of L-PGA in a radiation transparent container. The radiation transmissive container is not particularly limited, and for example, a glass container such as a glass vial can be used.
L−PGAの溶液を放射線透過性容器に入れた後は、そのまま放射線を照射してもよいが、予め、当該溶液に対して窒素を用いてバブリングしておくことが好ましい。当該溶液中に含有される酸素を除去することで、架橋反応の阻害を防ぐことができる。 After putting the L-PGA solution in the radiation transmissive container, radiation may be applied as it is, but it is preferable to bubble the solution beforehand using nitrogen. By removing oxygen contained in the solution, inhibition of the crosslinking reaction can be prevented.
なお、L−PGAの架橋に架橋剤を用いる場合は、エポキシ化合物、カルボン酸基及び/又はカルボキシレート基を含有する多糖、アミノ酸等、従来公知の架橋剤を用いればよく、特に限定されるものではない。例えば、エポキシ化合物としては、グリセリントリグリシジルエーテル、ジ−グリセリンポリグリシジルエーテル、ポリ−グリセリンポリグリシジルエーテル、ポリオキシエチレンソルビトールポリグリシジルエーテル、多糖類としては、グルコースとフルクトースとガラクトースとグルクロン酸とからなる混合物、ラムノースとグルコースとガラクトースとグルクロン酸とからなる混合物、及びヒアルロン酸を主成分とするポリカルボン酸、アミノ酸としては、ポリアスパラギン酸、ポリリシン、アスパラギン酸、リシン、アルギニン、及びこれらの混合物が挙げられる。これらは単独で用いてもよく、適宜2種類以上を混合して用いてもよい。 In addition, when using a crosslinking agent for crosslinking of L-PGA, a conventionally known crosslinking agent such as an epoxy compound, a polysaccharide containing a carboxylic acid group and / or a carboxylate group, an amino acid, etc. may be used, and is particularly limited. is not. For example, the epoxy compound includes glycerin triglycidyl ether, di-glycerin polyglycidyl ether, poly-glycerin polyglycidyl ether, polyoxyethylene sorbitol polyglycidyl ether, and the polysaccharide includes glucose, fructose, galactose, and glucuronic acid. Mixtures, mixtures of rhamnose, glucose, galactose, and glucuronic acid, and polycarboxylic acids based on hyaluronic acid, amino acids include polyaspartic acid, polylysine, aspartic acid, lysine, arginine, and mixtures thereof It is done. These may be used singly or may be used in combination of two or more.
上述のL−PGA架橋体の製造方法で用いるL−PGAとしては、L−PGAの分子同士が架橋することができる限り、限定されるものではないが、上述の通り、平均分子量が大きいL−PGAであることが好ましい。 The L-PGA used in the above-mentioned method for producing a crosslinked L-PGA is not limited as long as L-PGA molecules can be crosslinked with each other. However, as described above, L-PGA having a large average molecular weight is used. PGA is preferable.
また、 上述のL−PGA架橋体の製造方法に用いるL−PGAは、塩の状態であってもよく、例えばナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩等を用いることができる。中でも、ナトリウム塩が好ましい。 Moreover, L-PGA used for the manufacturing method of the above-mentioned L-PGA crosslinked body may be in the state of a salt, for example, sodium salt, potassium salt, magnesium salt, calcium salt etc. can be used. Of these, sodium salts are preferred.
上述のL−PGA架橋体の製造方法で用いるL−PGAとしては、従来公知の種々の方法で得たL−PGAを用いればよく、例えば、L−PGAを生産する微生物を用いて得たL−PGAを用いればよい。 As the L-PGA used in the above-described method for producing a crosslinked L-PGA, L-PGA obtained by various conventionally known methods may be used. For example, L-PGA obtained by using a microorganism that produces L-PGA. -PGA may be used.
化粧品組成物中のL−PGA架橋体の添加量は、L−PGA架橋体の有する作用を損なわない範囲で添加すれば良く、通常0.001〜50質量%が好ましく、0.01〜30質量%がより好ましく、0.1〜10質量%がさらに好ましく、0.5〜5質量%が特に好ましい。 What is necessary is just to add the addition amount of the L-PGA crosslinked body in a cosmetic composition in the range which does not impair the effect | action which L-PGA crosslinked body has, Usually 0.001-50 mass% is preferable, 0.01-30 mass % Is more preferable, 0.1 to 10% by mass is further preferable, and 0.5 to 5% by mass is particularly preferable.
発明の化粧品組成物は、L−PGA架橋体以外に、紫外線吸収剤を含有する。紫外線吸収剤としては、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、ケイ皮酸系紫外線吸収剤、トリアジン系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤などを使用しても良い。 The cosmetic composition of the invention contains an ultraviolet absorber in addition to the L-PGA crosslinked product. As UV absorbers, use benzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, triazine UV absorbers, benzophenone UV absorbers, etc. Also good.
紫外線吸収剤としては、安息香酸アミル、パラアミノ安息香酸オクチル、サリチル酸エチレングリコール、サリチル酸フェニル、サリチル酸オクチル、サリチル酸ベンジル、サリチル酸ブチルフェニル、サリチル酸ホモメンチル、ケイ皮酸ベンジル、パラメトキシケイ皮酸2−エトキシエチル、パラメトキシケイ皮酸オクチル、ジパラメトキシケイ皮酸モノ2−エチルヘキサン酸グリセリル、パラメトキシケイ皮酸イソプロピル、ジイソプロピル・ジイソプロピルケイ皮酸エステル混合物、ウロカニン酸、ウロカニン酸エチル、ヒドロキシメトキシベンゾフェノン、ヒドロキシメトキシベンゾフェノンスルホン酸およびその塩、ジヒドロキシメトキシベンゾフェノン、ジヒドロキシメトキシベンゾフェノンジスルフォン酸ナトリウム、ジヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、4−tert−ブチル−4’−メトキシ−ジベンゾイルメタン、2、4、6−トリアニリノ−p−(カルボ−2’−エチルヘキシル−1’−オキシ)−1、3、5−トリアジン、2−(2−ヒドロキシ−5−メチルフェニル)ベンゾトリアゾール、パラジメチルアミノ安息香酸2−エチルヘキシル、パラアミノ安息香酸エチル、トプチルメトキシジペンゾイルメタン、オキシベンゾン−1、グアイアズレンスルホン酸エチル、酸化亜鉛、シノキサート、ホモメンチル−N−アセチルアントラニレートなどが例示される。 Examples of the ultraviolet absorber include amyl benzoate, octyl paraaminobenzoate, ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, butylphenyl salicylate, homomenthyl salicylate, benzyl cinnamate, 2-ethoxyethyl paramethoxycinnamate, Octyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, isopropyl paramethoxycinnamate, diisopropyl diisopropylcinnamate ester mixture, urocanic acid, ethyl urocanate, hydroxymethoxybenzophenone, hydroxymethoxy Benzophenonesulfonic acid and its salts, dihydroxymethoxybenzophenone, dihydroxymethoxybenzophenone sodium disulfonate, dihydride Xylbenzophenone, tetrahydroxybenzophenone, 4-tert-butyl-4′-methoxy-dibenzoylmethane, 2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) -1,3, 5-triazine, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-ethylhexyl paradimethylaminobenzoate, ethyl paraaminobenzoate, topylmethoxydipenzoylmethane, oxybenzone-1, ethyl guaiazulenesulfonate, oxidation Examples thereof include zinc, sinoxate, and homomenthyl-N-acetylanthranilate.
これらの紫外線吸収剤は、1種を単独で、若しくは2種以上を組み合わせて用いることができる。 These ultraviolet absorbers can be used alone or in combination of two or more.
本発明に用いる紫外線吸収剤の配合量は、特に限定されていないが、本発明における組成物の全量に対し、0.01重量%以上50重量%以下が良く、好ましくは0.1重量%以上30重量%以下が良く、さらに好ましくは0.5重量%以上20重量%以下が良い。 The blending amount of the ultraviolet absorber used in the present invention is not particularly limited, but is preferably 0.01% by weight or more and 50% by weight or less, preferably 0.1% by weight or more, based on the total amount of the composition in the present invention. It is preferably 30% by weight or less, more preferably 0.5% by weight or more and 20% by weight or less.
本発明の化粧品組成物は、上記のL−PGA架橋体以外に、抗菌剤を含有してもよい。抗菌剤は、有機系抗菌剤および/または無機系抗菌剤であってもよい。 The cosmetic composition of the present invention may contain an antibacterial agent in addition to the above L-PGA crosslinked body. The antibacterial agent may be an organic antibacterial agent and / or an inorganic antibacterial agent.
抗菌剤としては、オウバク抽出液、ハロカルバン、クロロフェネシン、塩化リゾチーム、塩酸アルキルジアミノエチルグリシン、イソプロピルメチルフェノール、チモール、ヘキサクロロフェン、ベルベリン、チオキソロン、サリチル酸およびそれらの誘導体、安息香酸、安息香酸ナトリウム、パラオキシ安息香酸エステル、パラクロルメタクレゾール、塩化ベンザルコニウム、フェノキシエタノール、イソプロピルメチルフェノール、石炭酸、ソルビン酸、ソルビン酸カリウム、ヘキサクロロフェン、塩化クロルヘキシジン、トリクロロカルバニリド、感光素、ビス(2−ピリジルチオ−1−オキシド)亜鉛、チアントール、ヒノキチオール、トリクロサン、トリクロロヒドロキシジフェニルエーテル、クロルヘキシジングルコン酸塩、フェノキシエタノール、レゾルシン、アズレン、サリチル酸、ジンクピリチオン、モノニトログアヤコールナトリウム、ウイキョウエキス、サンショウエキス、塩化セチルピリジニウム、塩化ベンゼトニウム及びウンデシレン酸誘導体などが例示される。 Antibacterial agents include alum extract, halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, thymol, hexachlorophene, berberine, thioxolone, salicylic acid and their derivatives, benzoic acid, sodium benzoate , Paraoxybenzoic acid ester, parachlormetacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, carboxylic acid, sorbic acid, potassium sorbate, hexachlorophene, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, bis (2-pyridylthio) -1-oxide) zinc, thianthol, hinokitiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, Bruno butoxyethanol, resorcinol, azulene, salicylic acid, zinc pyrithione, sodium mononitroguayacol, fennel extract, pepper extract, cetylpyridinium chloride, etc. benzethonium chloride and undecylenic acid derivatives.
これらの抗菌剤は、1種を単独で、若しくは2種以上を組み合わせて用いることができる。 These antibacterial agents can be used alone or in combination of two or more.
本発明に用いる抗菌剤の配合量は、特に限定されていないが、本発明における組成物の全量に対し、0.001重量%以上10重量%以下が良く、好ましくは0.01重量%以上8重量%以下が良く、さらに好ましくは0.05重量%以上5重量%以下が良い。 The blending amount of the antibacterial agent used in the present invention is not particularly limited, but is preferably 0.001% by weight or more and 10% by weight or less, and preferably 0.01% by weight or more and 8% or less, based on the total amount of the composition in the present invention. % By weight or less is preferable, more preferably 0.05% by weight or more and 5% by weight or less.
L−PGA架橋体を含有する化粧品組成物の形態は特に制限されない。したがって、固体、液体、ペースト、ゼリー、粉末などのいずれの状態をとるものであってもよい。このような状態を形成するために、例えばゲル化剤を用いて固化したり、液体を用いて分散状態にしたりすることができる。また、溶媒を添加して溶液にしたり、噴霧乾燥して粉末状にしたりすることもできる。 The form of the cosmetic composition containing the L-PGA crosslinked product is not particularly limited. Therefore, it may take any state such as solid, liquid, paste, jelly, and powder. In order to form such a state, it can be solidified using, for example, a gelling agent, or can be dispersed using a liquid. Moreover, a solvent can be added to make a solution, or it can be spray-dried to form a powder.
本発明のL−PGA架橋体を含有する化粧品組成物は、優れた保湿効果、増粘作用及び毛髪改善作用を有しており、皮膚表面に適度な潤いを与えてハリとツヤを保つことが確認されている。 The cosmetic composition containing the L-PGA cross-linked product of the present invention has an excellent moisturizing effect, thickening action and hair improving action, and can impart appropriate moisture to the skin surface to keep it firm and shiny. It has been confirmed.
例えば、本発明のL−PGA架橋体を含有する化粧品組成物は化粧品として使用することができる。化粧品としては、化粧石鹸、シャンプー、洗顔料、リンス、アイクリーム、アイシャドウ、クリーム・乳液、化粧水、香水、おしろい、化粧油、頭髪用化粧品、染毛料、練香水、パウダー、パック、クレンジングクリーム、ひげそり用クリーム、ひげそり用ローション、日焼けオイル、日焼け止めオイル、日焼けローション、日焼け止めローション、日焼けクリーム、日焼け止めクリーム、ファンデーション、粉末香水、ほお紅、マスカラ、眉墨、爪クリーム、美爪エナメル、美爪エナメル除去液、洗毛料、浴用化粧品、口紅、リップクリーム、アイライナー、歯磨き、デオドラント剤、オーデコロン、養毛剤および育毛剤などが例示される。また、本発明のL−PGA架橋体を含有する化粧品組成物は、軟膏剤や湿布剤などとして使用することもできる。 For example, a cosmetic composition containing the L-PGA crosslinked product of the present invention can be used as a cosmetic. Cosmetics include cosmetic soap, shampoo, facial cleanser, rinse, eye cream, eye shadow, cream / milky lotion, lotion, perfume, funny, cosmetic oil, hair cosmetics, hair dye, paste perfume, powder, pack, cleansing cream , Shaving cream, shaving lotion, tanning oil, sunscreen oil, tanning lotion, sunscreen lotion, tanning cream, sunscreen cream, foundation, powdered perfume, blusher, mascara, eyebrow, nail cream, beautiful nail enamel, beautiful nails Examples include enamel remover, hair wash, bath cosmetic, lipstick, lip balm, eyeliner, toothpaste, deodorant, eau de cologne, hair nourishing agent, and hair restorer. The cosmetic composition containing the L-PGA crosslinked product of the present invention can also be used as an ointment or a poultice.
本発明のL−PGA架橋体を含有する化粧品組成物は、化粧品以外に、医薬部外品、医療用品、衛生用品、医薬品に配合して利用されることができる。 The cosmetic composition containing the L-PGA crosslinked product of the present invention can be used in combination with quasi-drugs, medical supplies, hygiene products, and pharmaceuticals in addition to cosmetics.
本発明のL−PGA架橋体を含有する化粧品組成物を、医薬部外品、医療用品、衛生用品、医薬品の形態で実施する場合、剤形は限定されず、アンプル、カプセル、粉末、顆粒、丸剤、錠剤、固形剤、液剤、ゲル、気泡、乳液、クリーム、軟膏、シート、ムース、浴用剤など多様なものとすることができる。 When the cosmetic composition containing the L-PGA cross-linked product of the present invention is implemented in the form of a quasi-drug, medical product, hygiene product, or pharmaceutical product, the dosage form is not limited and ampules, capsules, powders, granules, Various forms such as pills, tablets, solids, liquids, gels, bubbles, emulsions, creams, ointments, sheets, mousses, bathing agents and the like can be used.
医薬部外品、医療用品、衛生用品、医薬品としては、例えば内用・外用薬用製剤、化粧水、乳液、クリーム、軟膏、ローション、オイル、パックなどの基礎化粧料、洗顔料や皮膚洗浄料、シャンプー、リンス、ヘアートリートメント、ヘアクリーム、ポマード、ヘアスプレー、整髪料、パーマ剤、ヘアートニック、染毛料、育毛・養毛料などの頭髪化粧料、ファンデーション、白粉、おしろい、口紅、頬紅、アイシャドウ、アイライナー、マスカラ、眉墨、まつ毛などのメークアップ化粧料、美爪料などの仕上げ用化粧料、香水類、浴用剤、その他、歯磨き類、口中清涼剤・含嗽剤、液臭・防臭防止剤、衛生用品、衛生綿類、ウエットティシュなどが挙げられる。また、本発明のL−PGA架橋体を含有する化粧品組成物は、軟膏剤や湿布剤などとして使用することもできる。 As quasi-drugs, medical supplies, hygiene products, and pharmaceuticals, for example, internal and external pharmaceutical preparations, skin lotions, emulsions, creams, ointments, lotions, oils, packs, and other basic cosmetics, facial cleansers and skin cleansers, Hair cosmetics such as shampoo, rinse, hair treatment, hair cream, pomade, hair spray, hair conditioner, permanent agent, hair nick, hair dye, hair growth and hair restorer, foundation, white powder, funny, lipstick, blusher, eye shadow, Makeup cosmetics such as eyeliner, mascara, eyebrows, eyelashes, cosmetics for finishing such as nail care, perfumes, bath preparations, toothpastes, mouth fresheners, gargles, liquid odors and deodorants, Sanitary goods, sanitary cotton, wet tissue and the like. The cosmetic composition containing the L-PGA crosslinked product of the present invention can also be used as an ointment or a poultice.
本発明のL−PGA架橋体を含有する化粧品組成物は、ヒトに対して好適に適用されるものであるが、それぞれの作用効果が期待できる限り、ヒト以外の動物に対して適用することもできる。 The cosmetic composition containing the L-PGA cross-linked product of the present invention is suitably applied to humans, but may be applied to animals other than humans as long as each effect can be expected. it can.
本発明のL−PGA架橋体を含有する化粧品組成物は、必要に応じて本発明の効果を損なわない範囲内で、医薬部外品 、医療用品、衛生用品、医薬品に使用される成分や添加剤を併用して配合することができる。 The cosmetic composition containing the L-PGA cross-linked product of the present invention contains ingredients and additives used in quasi-drugs, medical products, hygiene products, and pharmaceuticals as long as the effects of the present invention are not impaired as necessary. An agent can be used in combination.
例えば、界面活性剤としては、アニオン界面活性剤(カルボン酸塩、スルホン酸塩、硫酸エステル塩、リン酸エステル塩)、カチオン界面活性剤(アミン塩、四級アンモニウム塩)、両性界面活性剤(カルボン酸型両性界面活性剤、硫酸エステル型両性界面活性剤、スルホン酸型両性界面活性剤、リン酸エステル型両性界面活性剤)、非イオン界面活性剤(エーテル型非イオン界面活性剤、エーテルエステル型非イオン界面活性剤、エステル型非イオン界面活性剤、ブロックポリマー型非イオン界面活性剤、含窒素型非イオン界面活性剤)、その他の界面活性剤(天然界面活性剤、タンパク質加水分解物の誘導体、高分子界面活性剤、チタン・ケイ素を含む界面活性剤、フッ化炭素系界面活性剤、などが挙げられる。 For example, as the surfactant, anionic surfactant (carboxylate, sulfonate, sulfate ester salt, phosphate ester salt), cationic surfactant (amine salt, quaternary ammonium salt), amphoteric surfactant ( Carboxylic acid type amphoteric surfactant, sulfate ester type amphoteric surfactant, sulfonic acid type amphoteric surfactant, phosphate ester type amphoteric surfactant), nonionic surfactant (ether type nonionic surfactant, ether ester) Type nonionic surfactant, ester type nonionic surfactant, block polymer type nonionic surfactant, nitrogen-containing type nonionic surfactant), other surfactants (natural surfactants, protein hydrolysates) Derivatives, polymer surfactants, surfactants containing titanium and silicon, fluorocarbon surfactants, and the like.
非イオン界面活性剤としては、例えば、ソルビタン脂肪酸エステル類(例えば、ソルビタンモノオレエート、ソルビタンモノイソステアレート、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンセスキオレエート、ソルビタントリオレエート、ペンタ−2−エチルヘキシル酸ジグリセロールソルビタン、テトラ−2−エチルヘキシル酸ジグリセロールソルビタン等);グリセリンポリグリセリン脂肪酸類(例えば、モノ綿実油脂肪酸グリセリン、モノエルカ酸グリセリン、セスキオレイン酸グリセリン、モノステアリン酸グリセリン、α,α’−オレイン酸ピログルタミン酸グリセリン、モノステアリン酸グリセリンリンゴ酸等);プロピレングリコール脂肪酸エステル類(例えば、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等が挙げられる。 Nonionic surfactants include, for example, sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate). Glycerol, penta-2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, etc.); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, glyceryl monostearate) , Α, α′-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.); propylene glycol fatty acid esters (for example, monos Propylene glycol tea acrylate, etc.); hardened castor oil derivative; glycerin alkyl ether and the like.
POE系の親水性非イオン界面活性剤としては、例えば、POE−ソルビタン脂肪酸エステル類(例えば、POE−ソルビタンモノオレエート、POE−ソルビタンモノステアレート、POE−ソルビタンモノオレエート、POE−ソルビタンテトラオレエート等);POEソルビット脂肪酸エステル類(例えば、POE−ソルビットモノラウレート、POE−ソルビットモノオレエート、POE−ソルビットペンタオレエート、POE−ソルビットモノステアレート等);POE−グリセリン脂肪酸エステル類(例えば、POE−グリセリンモノステアレート、POE−グリセリンモノイソステアレート、POE−グリセリントリイソステアレート等のPOE−モノオレエート等);POE−脂肪酸エステル類(例えば、POE−ジステアレート、POE−モノジオレエート、ジステアリン酸エチレングリコール等);POE−アルキルエーテル類(例えば、POE−ラウリルエーテル、POE−オレイルエーテル、POE−ステアリルエーテル、POE−ベヘニルエーテル、POE−2−オクチルドデシルエーテル、POE−コレスタノールエーテル等);プルロニック型類(例えば、プルロニック等);POE・POP−アルキルエーテル類(例えば、POE・POP−セチルエーテル、POE・POP−2−デシルテトラデシルエーテル、POE・POP−モノブチルエーテル、POE・POP−水添ラノリン、POE・POP−グリセリンエーテル等);テトラPOE・テトラPOP−エチレンジアミン縮合物類(例えば、テトロニック等);POE−ヒマシ油硬化ヒマシ油誘導体(例えば、POE−ヒマシ油、POE−硬化ヒマシ油、POE−硬化ヒマシ油モノイソステアレート、POE−硬化ヒマシ油トリイソステアレート、POE−硬化ヒマシ油モノピログルタミン酸モノイソステアリン酸ジエステル、POE−硬化ヒマシ油マレイン酸等);POE−ミツロウ・ラノリン誘導体(例えば、POE−ソルビットミツロウ等);アルカノールアミド(例えば、ヤシ油脂肪酸ジエタノールアミド、ラウリン酸モノエタノールアミド、脂肪酸イソプロパノールアミド等);POE−プロピレングリコール脂肪酸エステル;POE−アルキルアミン;POE−脂肪酸アミド;ショ糖脂肪酸エステル;アルキルエトキシジメチルアミンオキシド;トリオレイルリン酸等が挙げられる。 Examples of the POE-based hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerol monostearate, POE-glycerin monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.); POE-fatty acid esters (for example, POE-distearate) POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether), POE-monodiolate, ethylene glycol distearate, etc. POE-cholestanol ether, etc.); Pluronic type (for example, Pluronic, etc.); POE • POP-alkyl ethers (for example, POE • POP-cetyl ether, POE • POP-2-decyltetradecyl ether, POE • POP−) Monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); tetra-POE / tetra-POP-ethylenediamine condensates (for example, Tetronic, etc.); POE-castor oil-cured castor Oil derivatives (eg POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE -Hardened castor oil maleic acid, etc.); POE-beeswax lanolin derivatives (eg POE-sorbite beeswax etc.); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide etc.); POE- Examples thereof include propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; trioleyl phosphate.
低級アルコールとしては、例えば、エタノール、プロパノール、イソプロパノール、イソブチルアルコール、t−ブチルアルコール、ラウリルアルコール、セタノール、ステアリルアルコール、オレイルアルコール等が挙げられる。 Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, lauryl alcohol, cetanol, stearyl alcohol, oleyl alcohol and the like.
多価アルコールとしては、例えば、2価のアルコール(例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、1,2−ブチレングリコール、1,3−ブチレングリコール、テトラメチレングリコール、2,3−ブチレングリコール、ペンタメチレングリコール、2−ブテン−1,4−ジオール、ヘキシレングリコール、オクチレングリコール等);3価のアルコール(例えば、グリセリン、トリメチロールプロパン等);4価アルコール(例えば、1,2,6−ヘキサントリオール等のペンタエリスリトール等);5価アルコール(例えば、キシリトール等);6価アルコール(例えば、ソルビトール、マンニトール等);多価アルコール重合体(例えば、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ポリプロピレングリコール、テトラエチレングリコール、ジグリセリン、ポリエチレングリコール、トリグリセリン、テトラグリセリン、ポリグリセリン等);2価のアルコールアルキルエーテル類(例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノ2−メチルヘキシルエーテル、エチレングリコールイソアミルエーテル、エチレングリコールベンジルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル等);2価アルコールアルキルエーテル類(例えば、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールブチルエーテル、ジエチレングリコールメチルエチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールイソプロピルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールエチルエーテル、ジプロピレングリコールブチルエーテル等);2価アルコールエーテルエステル(例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノフェニルエーテルアセテート、エチレングリコールジアジベート、エチレングリコールジサクシネート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノフェニルエーテルアセテート等);グリセリンモノアルキルエーテル(例えば、キミルアルコール、セラキルアルコール、バチルアルコール等);糖アルコール(例えば、ソルビトール、マルチトール、マルトトリオース、マンニトール、ショ糖、エリトリトール、グルコース、フルクトース、デンプン分解糖、マルトース、キシリトース、デンプン分解糖還元アルコール等);グリソリッド;テトラハイドロフルフリルアルコール;POE−テトラハイドロフルフリルアルコール;POP−ブチルエーテル;POP・POE−ブチルエーテル;トリポリオキシプロピレングリセリンエーテル;POP−グリセリンエーテル;POP−グリセリンエーテルリン酸;POP・POE−ペンタンエリスリトールエーテル、ポリグリセリン等が挙げられる。
高級アルコールとしては、例えば、ラウリルアルコール、セチルアルコール、ステアリルアルコール、ベヘニルアルコール、ミリスチルアルコール、オレイルアルコール、セトステアリルアルコール、ホホバアルコール、ラノリンアルコール、バチルアルコール、2−デシルテトラテセシノール、コレステロール、フィトステロール、イソステアリルアルコール等が挙げられる。
その他のアルコール類としては、コレステロール、フィトステロールなどの天然アルコール、2−ヘキシルデカノール、イソステアリルアルコール、2−オクチルドデカノールなどの合成アルコール類などが挙げられる。
Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1, 2, 6) Pentaerythritol such as hexanetriol, etc .; pentavalent alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, Tylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol) Monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Dibutyl Dihydric alcohol alkyl ethers (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol) Monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol Dibutyl alcohol ether ester (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazebate, ethylene glycol disuccine) Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ether (example) Sugar alcohol (eg, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, starch decomposition) Sugar-reduced alcohol, etc.); glycolide; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP / POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP · POE-pentane erythritol ether, polyglycerin and the like.
Examples of the higher alcohol include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, jojoba alcohol, lanolin alcohol, batyl alcohol, 2-decyltetrathececinol, cholesterol, phytosterol, and isostearyl. Alcohol etc. are mentioned.
Examples of other alcohols include natural alcohols such as cholesterol and phytosterol, and synthetic alcohols such as 2-hexyldecanol, isostearyl alcohol, and 2-octyldodecanol.
油類としては、アボカド油、オリーブ油、ゴマ油、ツバキ油、月見草油、タートル油、マカデミアンナッツ油、トウモロコシ油、ミンク油、ナタネ油、卵黄油、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、キリ油、ホホバ油、カカオ脂、ヤシ油、馬油、パーム油、パーム核油、牛脂、羊脂、豚脂、ラノリン、鯨ロウ、ミツロウ、カルナウバロウ、モクロウ、キャンデリラロウ、スクワラン等の動植物油およびその硬化油、流動パラフィン、ワセリン等の鉱物油、トリパルミチン酸グリセリン等の合成トリグリセリンが挙げられる。 Oils include avocado oil, olive oil, sesame oil, camellia oil, evening primrose oil, turtle oil, macadamian nut oil, corn oil, mink oil, rapeseed oil, egg yolk oil, persic oil, wheat germ oil, sasanca oil, castor oil , Linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, kiri oil, jojoba oil, cacao butter, palm oil, horse oil, palm oil, palm kernel oil , Beef tallow, sheep fat, lard, lanolin, whale wax, beeswax, carnauba wax, molasses, candelilla wax, squalane, etc. and its hardened oil, mineral oils such as liquid paraffin, petrolatum, synthesis of glycerin tripalmitate, etc. Triglycerin is mentioned.
脂肪酸類としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、オレイン酸、12−ヒドロキシステアリン酸、ウンデシレン酸、トール油、ラノリン脂肪酸などの天然脂肪酸、イソノナン酸、カプロン酸、2−エチルブタン酸、イソペンタン酸、2−メチルペンタン酸、2−エチルヘキサン酸、イソペンタン酸などの合成脂肪酸が挙げられる。また、それら以外の高級脂肪酸としては、例えばリノール酸、リノレン酸、イソステアリン酸、エイコサペンタエン酸、ドコサヘキサエン酸などが挙げられる。 Examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tall oil, lanolin fatty acid and other natural fatty acids, isononanoic acid, caproic acid, 2- Synthetic fatty acids such as ethyl butanoic acid, isopentanoic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid and isopentanoic acid are exemplified. Examples of other higher fatty acids include linoleic acid, linolenic acid, isostearic acid, eicosapentaenoic acid, and docosahexaenoic acid.
例えば、エステル類としては、ミリスチン酸イソプロピル、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、オレイン酸オレイル、オレイン酸デシル、ミリスチン酸オクチルドデシル、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、フタル酸ジエチル、フタル酸ジブチル、酢酸ラノリン、モノステアリン酸エチレングリコール、モノステアリン酸プロピレングリコール、ジオレイン酸プロピレングリコール、オクタン酸セチル、ミリスチン酸オクチルドデシル、ミリスチン酸イソプロピル、ミリスチン酸ミリスチル、パルミチン酸イソプロピル、ステアリン酸ブチル、ジメチルオクタン酸、などが挙げられる。
シリコーンとしては、例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン等の鎖状ポリシロキサン、デカメチルシクロポリシロキサン等の環状ポリシロキサン、シリコーン樹脂等の三次元網目構造のもの等が挙げられる。
For example, esters include isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyl decyl dimethyloctanoate, cetyl lactate, lactic acid Myristyl, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, cetyl octanoate, octyldodecyl myristate, isopropyl myristate, myristyl myristate, isopropyl palmitate , Butyl stearate, dimethyloctanoic acid, and the like.
Examples of silicone include chain polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as decamethylcyclopolysiloxane, and three-dimensional network structures such as silicone resins.
例えば、ロウ類としては、ミツロウ、カルナバロウ、鯨ロウ、ラノリン、液状ラノリン、還元ラノリン、硬質ラノリン、カンデリラロウ、モンタンロウ、セラックロウなどが挙げられる。 Examples of waxes include beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, montan wax, shellac wax, and the like.
例えば、鉱物油としては、流動パラフィン、ワセリン、パラフィン、オゾケライド、セレシン、マイクロクリスタンワックス、ポリエチレン末、スクワレン、スクワラン、プリスタンなどが挙げられる。 Examples of mineral oils include liquid paraffin, petrolatum, paraffin, ozokelide, ceresin, microcristan wax, polyethylene powder, squalene, squalane, and pristane.
例えば、金属セッケンとしては、ステアリン酸アルミニウム、ステアリン酸マグネシウム、ステアリン酸亜鉛、ステアリン酸カルシウム、パルミチン酸亜鉛、ミリスチン酸マグネシウム、ラウリン酸亜鉛、ウンデシレン酸亜鉛などが挙げられる。 For example, examples of the metal soap include aluminum stearate, magnesium stearate, zinc stearate, calcium stearate, zinc palmitate, magnesium myristate, zinc laurate, and zinc undecylate.
例えば、ガム質および水溶性高分子化合物としては、アラビアゴム、ベンゾインゴム、ダンマルゴム、グアヤク脂、アイルランド苔、カラヤゴム、トラガントゴム、キャロブゴム、クインシード、寒天、カゼイン、デキストリン、ゼラチン、ペクチン、デンプン、カラギーナン、カルボキシアルキルキチン、キトサン、ヒドロキシアルキルキチン、低分子キトサン、キトサン塩、硫酸化キチン、リン酸化キチン、アルギン酸およびその塩、ヒアルロン酸およびその塩、コンドロイチン硫酸、ヘパリン、エチルセルロース、メチルセルロース、カルボキシメチルセルロース、カルボキシエチルセルロース、カルボキシエチルセルロースナトリウム、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ニトロセルロース、結晶セルロース、ポリビニルアルコール、ポリビニルメチルエーテル、ポリビニルピロリドン、ポリビニルメタアクリレート、ポリアクリル酸塩、ポリエチレンオキサイドやポリプロピレンオキサイド等のポリアルキレンオキサイドまたはその架橋重合物、カルボキシビニルポリマー、ポリエチレンイミンなどが挙げられる。 For example, gum and water-soluble polymer compounds include gum arabic, benzoin gum, danmar gum, guaiac oil, Irish moss, Karaya gum, tragacanth gum, carob gum, quinseed, agar, casein, dextrin, gelatin, pectin, starch, carrageenan, Carboxyalkylchitin, chitosan, hydroxyalkylchitin, low molecular chitosan, chitosan salt, sulfated chitin, phosphorylated chitin, alginic acid and its salt, hyaluronic acid and its salt, chondroitin sulfate, heparin, ethylcellulose, methylcellulose, carboxymethylcellulose, carboxyethylcellulose , Sodium carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, nitrocellulose, crystalline cellulose Scan, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyl methacrylate, polyacrylic acid salts, polyalkylene oxide or crosslinked polymer thereof such as polyethylene oxide or polypropylene oxide, carboxyvinyl polymers, such as polyethyleneimine.
例えば、ビタミン類としては、ビタミンA群ではレチノール、レチナール(ビタミンA1)、デヒドロレチナール(ビタミンA2)、カロチン、リコピン(プロビタミンA)、ビタミンB群では、チアミン塩酸塩、チアミン硫酸塩(ビタミンB1)、リボフラビン(ビタミンB2)、ピリドキシン(ビタミンB6)、シアノコバラミン(ビタミンB12)、葉酸類、ニコチン酸類、パントテン酸類、ビオチン類、コリン、イノシトール類、ビタミンC群では、アスコルビン酸およびその誘導体、ビタミンD群では、エルゴカルシフェロール(ビタミンD2)、コレカルシフェロール(ビタミンD3)、ジヒドロタキステロール、ビタミンE群では、トコフェロールおよびその誘導体、ユビキノン類、ビタミンK群では、フィトナジオン(ビタミンK1)、メナキノン(ビタミンK2)、メナジオン(ビタミンK3)、メナジオール(ビタミンK4)などが挙げられる。 For example, as vitamins, retinol, retinal (vitamin A1), dehydroretinal (vitamin A2), carotene, lycopene (provitamin A), vitamin B group, thiamine hydrochloride, thiamine sulfate (vitamin B1) ), Riboflavin (vitamin B2), pyridoxine (vitamin B6), cyanocobalamin (vitamin B12), folic acid, nicotinic acids, pantothenic acids, biotins, choline, inositols, vitamin C, ascorbic acid and its derivatives, vitamin D In the group, ergocalciferol (vitamin D2), cholecalciferol (vitamin D3), dihydrotachysterol, in vitamin E group, tocopherol and its derivatives, ubiquinones, in vitamin K group, phytonadione (vita) Emissions K1), menaquinone (vitamin K2), menadione (vitamin K3), and the like menadiol (vitamin K4).
例えば、アミノ酸としては、バリン、ロイシン、イソロイシン、トレオニン、メチオニン、フェニルアラニン、トリプトファン、リジン、グリシン、アラニン、アスパラギン、グルタミン、セリン、システイン、シスチン、チロシン、プロリン、ヒドロキシプロリン、アスパラギン酸、グルタミン酸、ヒドロキシリジン、アルギニン、オルニチン、ヒスチジンなどや、それらの硫酸塩、リン酸塩、硝酸塩、クエン酸塩、あるいはピロリドンカルボン酸の如きアミノ酸誘導体などが挙げられる。 For example, amino acids include valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, glutamic acid, hydroxylysine , Arginine, ornithine, histidine, and the like, and sulfates, phosphates, nitrates, citrates, and amino acid derivatives such as pyrrolidone carboxylic acid.
例えば、動物あるいは植物、生薬の抽出物やエキスとしては、アセンヤク(阿仙薬)、アシタバ、アセロラ、アルテア、アルニカ、アボカド、アマチャ(甘茶)、アロエ、アロエベラ、イラクサ、イチョウ(銀杏葉、銀杏)、ウイキョウ(茴香)、ウコン(鬱金)、ウスバサイシン(細辛)、ウメ(烏梅)、ウラジロガシ、ウワウルシ、ノイバラ(営実)、ヒキオコシ(延命草)、オウギ(黄耆)、コガネバナ(オウゴン)、ヤマザクラ(桜皮
)、キハダ(黄柏)、オウレン(黄連)、オタネニンジン(人参)、オトギリソウ(弟切草)、オドリコソウ、オランダガラシ、オレンジ、イトヒメハギ(遠志)、ウツボグサ(夏枯草)、ツルドクダミ(何首烏)、エンジュ(槐花)、ヨモギ(ガイ葉)、ガジュツ(莪朮)、クズ(葛根)、カノコソウ(吉草根)、カミツレ、キカラスウリ(瓜呂根)、カワラヨモギ(茵チン蒿)、カンゾウ(甘草)、フキタンポポ(款冬花、款冬葉)、キイチゴ、キウイ果実、キキョウ(桔梗)、キク(菊花)、キササゲ(梓実)、ミカン属植物果実(枳実)、タチバナ(橘皮)、キュウリ、ウドまたはシシウド(羌活、独活)、アンズ(杏仁)、クコ(地骨皮、枸杞子、枸杞葉)、クララ(苦参)、クスノキ、クマザサ、グレープフルーツ果実、ニッケイ(桂皮)、ケイガイ(ケイガイ)、エビスグサ(決明子)、マルバアサガオまたはアサガオ(ケン牛子)、ベニバナ(紅花)、ゴバイシ(五倍子)、コンフリー、コパイバ、クチナシ(山梔子)、ゲンチアナ、ホオノキ(厚朴)、ヒナタイノコズチ(牛膝)、ゴシュユ(呉茱萸)、ゴボウ、チョウセンゴミシ(五味子)、米、米ぬか、コムギ、ミシマサイコ(柴胡)、サフラン、サボンソウ、サンザシ(山ザ子)、サンショウ(山椒)、サルビア、サンシチニンジン(三七人参)、シイタケ(椎茸)、ジオウ(地黄)、シクンシ(使君子)、ムラサキ(紫根)、シソ(紫蘇葉、紫蘇子)、カキ(柿蒂)、シャクヤク(芍薬)、オオバコ(車前子、車前草)、ショウガ(生姜)、ショウブ(菖蒲)、トウネズミモチ(女貞子)、シモツケソウ、シラカバ、スイカズラ(金銀花、忍冬)、セイヨウキヅタ、セイヨウノコギリソウ、セイヨウニワトコ、アズキ(赤小豆)、ニワトコ(接骨木)、ゼニアオイ、センキュウ(川キュウ)、センブリ(当薬)、クワ(桑白皮、桑葉)、ナツメ(大棗)、ダイズ、タラノキ、チクセツニンジン(竹節人参)、ハナスゲ(知母)、ワレモコウ(地楡)、ドクダミ(十薬)、フユムシナツクサタケ(冬虫夏草)、トウガラシ、ホオズキ(登呂根)、タチジャコウソウ、リョクチャ(緑茶)、コウチャ(紅茶)、チョウジ(丁子)、ウンシュウミカン(陳皮)、ツバキ、ツボクサ、トウガラシ(番椒)、トウキ(当帰)、トウキンセンカ、ダイダイ(橙皮)、ワレモコウ(地楡)、トウモロコシ(南蛮毛)、トチュウ(杜仲、杜仲葉)、トマト、ナンテン(南天実)、ニンニク(大サン)、オオムギ(麦芽)、ハクセン(白蘚皮)、ジャノヒゲ(麦門冬)、パセリ、バタタ、ハッカ(薄荷)、ハマメリス、バラ、ビワ葉(枇杷葉)、マツホド(茯リョウ)、ブドウまたはその葉、ヘチマ、ボダイジュ、ボタン(牡丹皮)、ホップ、マイカイ(マイ瑰花)、松葉、マロニエ、マンネンロウ、ムクロジ、メリッサ、メリロート、ボケ(木瓜)、モヤシ、モモ(桃仁、桃葉)、ヒオウギ(射干)、ビンロウジュ(檳ロウ子)、メハジキ(益母草)、ヤグルマギク、ユキノシタ(虎耳草)、ヤマモモ(楊梅皮)、ヤシャブシ(矢車)、ハトムギ(ヨクイニン)、モウコヨモギ、ヤマヨモギ、ラベンダー、リンゴ果実、マンネンタケ(霊芝)、レモン果実、レンギョウ(連翹)、レンゲソウ、ゲンノショウコ(老鸛草)、ハシリドコロ(ロート根)、鶏トサカ、牛・人の胎盤抽出物、豚・牛の胃、十二指腸、或いは腸の抽出物若しくはその分解物、水溶性コラーゲン、水溶性コラーゲン誘導体、コラーゲン加水分解物、エラスチン、エラスチン加水分解物、水溶性エラスチン誘導体、シルク蛋白、シルク蛋白分解物、牛血球蛋白分解物などが挙げられる。
For example, extracts or extracts of animals or plants and herbal medicines include Asenyaku (Asenyaku), Ashitaba, Acerola, Altea, Arnica, Avocado, Achacha (Amacha), Aloe, Aloe Vera, Nettle, Ginkgo (Ginkgo leaf, Ginkgo), Fennel (cage), turmeric (red gold), usba saishin (spicy), Japanese apricot (salmon plum), Japanese white beetle, walrus, green rose (fruit), hikikoshi (life-extending grass), Japanese oak (yellow cocoon), Koganebana (Ogon), Yamazakura ( Cherry bark), yellowfin, yellow orchid, ginseng, carrot, helicopter, licorice, holland garashi, orange, himehagi (distant), eel-brush (summer hay), tsurugokudami (what head-knot), enju (槐花), mugwort (guy leaf), scallops (莪 朮), kudu (kazune), kanoko Cormorant (Valgarine), Chamomile, Kikarasuuri (Gorne), Kawamomogi (Golden Chrysanthemum), Licorice (licorice), Japanese licorice (Cavity Winter Flower, Cicada Winter Leaves), Japanese Strawberry, Kiwi Fruit, Japanese Clover (Kikkyo), Chrysanthemum (Chrysanthemum Flower) ), Catalpa (fruit), Citrus genus fruit (fruit), Tachibana (tachibana skin), cucumber, Udo or Shishido (living, solitary), apricots, wolfberry (bone crust, coconut, coconut leaves) , Clara, bittersweet, Kumazasa, grapefruit fruit, Nikkei, Keikei, Ebisugusa, Maruba morning glory or morning glory (Ken bull), safflower (Safflower), Gobaishi (penta), Confrey , Copaiba, gardenia, gentian, honoki (shoku), hinata taikozu (cow knee), goshuyu (burdock), burdock, butterfly Ngomushi (Gomiko), Rice, Rice bran, Wheat, Mishima Saiko (Saiko), Saffron, Savonso, Hawthorn (Yamazako), Salamander (Samurai), Salvia, Sancynin carrot (Ginseng ginseng), Shiitake mushroom (Shiitake), Jiou (jihuang), Shikunshi (Mr. Kimiko), Murasaki (Shine), Perilla (Shiso leaf, Shiso), Oyster (柿蒂), Peonies (glaze), Psyllium (car forerunner, car front grass), Ginger (ginger), Shobu (Japanese cypress), Japanese horned potato (Sadako), Shimotsuke, Shiraba, Honeysuckle (Gin and silver flowers, Shinobu), Ivy, Achillea millefolium, Elderberry, Azuki (Red Azuki), Elderberry (Bone), Zeniaoi, Senkyu ), Assembly (this drug), mulberry (mulberry white skin, mulberry leaf), jujube (daegu), soybean, taranoki, chiketsu carrot (bamboo ginseng) ), Hanasuge (knowing mother), Waremokkou (earth), Dokudami (10 medicines), Fuyumushinatsusatake (Cycium cordyceps), chili pepper, physalis (Torone), Tachikakuso, Ryokucha (green tea), kocha (tea), clove (Clove), mandarin orange (Chen bark), camellia, camellia, capsicum (panju), crested sardine (Tochigi), red bellflower, daidai (orange peel), bituminous (ground), corn (southern fur), tochu (Tochu) , 杜 中葉), tomato, Nanten (Southern fruit), garlic (large sun), barley (malt), hakusen (white birch), janohi (barley winter), parsley, batata, mint (light load), hamamelis, rose , Loquat leaves, pine pods, grapes or their leaves, loofah, bodaiju, buttons (peony skin), hops, maikai , Matsuba, Maronie, Mannenrou, Mukuroji, Melissa, Merirot, Bokeh (Kiso), Palms, Peach (Peachin, Peach), Hiogi (Garden-dried), Binroju (Mellow wax), Swordfish (Mothera), Cornflower, Yukinoshita Grass), bayberry (Yellow Plum), Yashabushi (Yakuin), pearl barley (Yokuinin), mugwort, sagebrush, lavender, apple fruit, garlic mushroom (reishi), lemon fruit, forsythia (lily), forsythia, genus , Hashiridokoro (roth root), chicken tosaka, cattle / human placenta extract, pig / cow stomach, duodenum, or intestinal extract or its degradation product, water-soluble collagen, water-soluble collagen derivative, collagen hydrolyzate, Elastin, elastin hydrolyzate, water-soluble elastin derivative, silk protein, sill Protein hydrolyzate, and the like cow blood cell protein hydrolyzate.
例えば、微生物培養代謝物としては、酵母エキス、亜鉛含有酵母エキス、ゲルマニウム含有酵母エキス、セレン含有酵母エキス、マグネシウム含有酵母エキス、米醗酵エキス、ユーグレナ抽出物、脱脂粉乳の乳酸発酵物などが挙げられる。 Examples of microbial culture metabolites include yeast extract, zinc-containing yeast extract, germanium-containing yeast extract, selenium-containing yeast extract, magnesium-containing yeast extract, rice fermentation extract, Euglena extract, and lactic acid fermented milk powder. .
例えば、α−ヒドロキシ酸としては、グリコール酸、クエン酸、リンゴ酸、酒石酸、乳酸などが挙げられる。 For example, examples of the α-hydroxy acid include glycolic acid, citric acid, malic acid, tartaric acid, and lactic acid.
例えば、無機顔料としては、無水ケイ酸、ケイ酸マグネシウム、タルク、カオリン、ベントナイト、マイカ、雲母チタン、オキシ塩化ビスマス、酸化ジルコニウム、酸化マグネシウム、酸化亜鉛、酸化チタン、炭酸カルシウム、炭酸マグネシウム、黄酸化鉄、ベンガラ、黒酸化鉄、グンジョウ、酸化クロム、水酸化クロム、カーボンブラック、カラミンなどが挙げられる。 For example, inorganic pigments include anhydrous silicic acid, magnesium silicate, talc, kaolin, bentonite, mica, titanium mica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, yellow oxide Examples include iron, bengara, black iron oxide, gunjo, chromium oxide, chromium hydroxide, carbon black, and calamine.
例えば、収斂剤としては、乳酸、酒石酸、コハク酸、クエン酸、アラントイン、塩化亜鉛、硫酸亜鉛、酸化亜鉛、カラミン、p−フェノールスルホン酸亜鉛、硫酸アルミニウムカリウム、レソルシン、塩化第二鉄、タンニン酸などが挙げられる。 For example, astringents include lactic acid, tartaric acid, succinic acid, citric acid, allantoin, zinc chloride, zinc sulfate, zinc oxide, calamine, zinc p-phenolsulfonate, potassium aluminum sulfate, resorcin, ferric chloride, tannic acid Etc.
例えば、殺菌・消毒薬としては、アクリノール、イオウ、塩化ベンザルコニウム、塩化ベンゼトニウム、塩化メチルロザニリン、クレゾール、グルコン酸カルシウム、グルコン酸クロルヘキシジン、スルファミン、マーキュロクロム、ラクトフェリンまたはその加水分解物などが挙げられる。 Examples of the bactericidal / disinfectant include acrinol, sulfur, benzalkonium chloride, benzethonium chloride, methyl rosaniline chloride, cresol, calcium gluconate, chlorhexidine gluconate, sulfamine, mercurochrome, lactoferrin or a hydrolyzate thereof.
例えば、頭髪用剤としては、二硫化セレン、臭化アルキルイソキノリニウム液、ジンクピリチオン、ビフェナミン、チアントール、カスタリチンキ、ショウキョウチンキ、トウガラシチンキ、塩酸キニーネ、強アンモニア水、臭素酸カリウム、臭素酸ナトリウム、チオグリコール酸などが挙げられる。 For example, selenium disulfide, alkylisoquinolinium bromide, zinc pyrithione, biphenamine, thianthol, castari tincture, ginger tincture, pepper tincture, quinine hydrochloride, strong ammonia water, potassium bromate, sodium bromate And thioglycolic acid.
例えば、香料としては、ジャコウ、シベット、カストリウム、アンバーグリスなどの天然動物性香料、アニス精油、アンゲリカ精油、イラン精油、イリス精油、ウイキョウ精油、オレンジ精油、カナンガ精油、カラウェー精油、カルダモン精油、グアヤクウッド精油、クミン精油、黒文字精油、ケイ皮精油、シンナモン精油、ゲラニウム精油、コパイババルサム精油、コリアンデル精油、シソ精油、シダーウッド精油、シトロネラ精油、ジャスミン精油、ジンジャーグラス精油、杉精油、スペアミント精油、西洋ハッカ精油、大茴香精油、チュベローズ精油、丁字精油、橙花精油、冬緑精油、トルーバルサム精油、バチュリー精油、バラ精油、パルマローザ精油、檜精油、ヒバ精油、白檀精油、プチグレン精油、ベイ精油、ベチバ精油、ベルガモット精油、ペルーバルサム精油、ボアドローズ精油、芳樟精油、マンダリン精油、ユーカリ精油、ライム精油、ラベンダー精油、リナロエ精油、レモングラス精油、レモン精油、ローズマリー精油、和種ハッカ精油などの植物性香料、その他合成香料などが挙げられる。 For example, as perfumes, natural animal perfumes such as musk, civet, castorium, ambergris, anise essential oil, angelica essential oil, Iran essential oil, Iris essential oil, fennel essential oil, orange essential oil, cananga essential oil, caraway essential oil, cardamom essential oil, guayakwood essential oil , Cumin essential oil, black letter essential oil, cinnamon essential oil, cinnamon essential oil, geranium essential oil, copaiba balsam essential oil, coriandel essential oil, perilla essential oil, cedarwood essential oil, citronella essential oil, jasmine essential oil, gingergrass essential oil, cedar essential oil, spearmint essential oil, western peppermint essential oil , Otsuka perfume essential oil, tuberose essential oil, clove essential oil, orange flower essential oil, winter green essential oil, trout balsam essential oil, buttery essential oil, rose essential oil, palmarosa essential oil, persimmon essential oil, hiba essential oil, sandalwood essential oil, petitgren essential oil, bay essential oil, vetiva essential oil, bell Vegetable fragrances such as Mott essential oil, Peruvian balsam essential oil, Boad Rose essential oil, melamine essential oil, mandarin essential oil, eucalyptus essential oil, lime essential oil, lavender essential oil, linaloe essential oil, lemongrass essential oil, lemon essential oil, rosemary essential oil, Japanese seed mint essential oil, Other synthetic fragrances can be mentioned.
例えば、色素・着色剤としては、赤キャベツ色素、赤米色素、アカネ色素、アナトー色素、イカスミ色素、ウコン色素、エンジュ色素、オキアミ色素、柿色素、カラメル、金、銀、クチナシ色素、コーン色素、タマネギ色素、タマリンド色素、スピルリナ色素、ソバ全草色素、チェリー色素、海苔色素、ハイビスカス色素、ブドウ果汁色素、マリーゴールド色素、紫イモ色素、紫ヤマイモ色素、ラック色素、ルチンなどが挙げられる。 For example, as a dye / colorant, a red cabbage dye, a red rice dye, an akane dye, an anato dye, an squid dye, a turmeric dye, an enju dye, a krill dye, an amber dye, a caramel, a gold, a silver, a gardenia dye, a corn dye, Examples include onion pigment, tamarind pigment, spirulina pigment, buckwheat whole plant pigment, cherry pigment, laver pigment, hibiscus pigment, grape juice pigment, marigold pigment, purple potato pigment, purple yam pigment, lac pigment and rutin.
例えば、甘味料としては、砂糖、甘茶、果糖、アラビノース、ガラクトース、キシロース、マンノース、麦芽糖、蜂蜜、ブドウ糖、ミラクリン、モネリンなどが挙げられる。 Examples of sweeteners include sugar, sweet tea, fructose, arabinose, galactose, xylose, mannose, maltose, honey, glucose, miraculin, monelin and the like.
例えば、栄養強化剤としては、貝殻焼成カルシウム、シアノコラバミン、酵母、小麦胚芽、大豆胚芽、卵黄粉末、ヘミセルロース、ヘム鉄などが挙げられる。 For example, examples of the nutrient fortifier include shell calcined calcium, cyanocolabamine, yeast, wheat germ, soybean germ, egg yolk powder, hemicellulose, heme iron and the like.
本発明のL−PGA架橋体を含有する化粧品組成物に配合することができる成分や添加剤としては、その他、ホルモン類、金属イオン封鎖剤、pH調整剤、キレート剤、防腐・防バイ剤、清涼剤、安定化剤、乳化剤、動・植物性蛋白質およびその分解物、動・植物性多糖類およびその分解物、動・植物性糖蛋白質およびその分解物、血流促進剤、消炎剤・抗アレルギー剤、細胞賦活剤、角質溶解剤、創傷治療剤、増泡剤、増粘剤、口腔用剤、消臭・脱臭剤、苦味料、調味料、酵素などが挙げられる。 Other ingredients and additives that can be blended in the cosmetic composition containing the L-PGA crosslinked product of the present invention include hormones, sequestering agents, pH adjusters, chelating agents, antiseptic and antibacterial agents, Coolant, stabilizer, emulsifier, animal / plant protein and its degradation product, animal / plant polysaccharide and its degradation product, animal / plant glycoprotein and its degradation product, blood flow promoter, anti-inflammatory agent / anti Examples include allergic agents, cell activators, keratolytic agents, wound treatment agents, foaming agents, thickeners, oral preparations, deodorizing / deodorizing agents, bittering agents, seasonings, enzymes, and the like.
本発明のL−PGA架橋体を含有する化粧品組成物は、保湿効果、増粘作用、毛髪改善作用などが必要とされる場合に広く使用することができる。使用量は、所期の保湿効果、増粘作用、毛髪改善作用などを十分に奏する範囲内で決定する。 The cosmetic composition containing the L-PGA crosslinked product of the present invention can be widely used when a moisturizing effect, a thickening effect, a hair improving effect and the like are required. The amount to be used is determined within a range in which the desired moisturizing effect, thickening effect, hair improving effect and the like are sufficiently exhibited.
本発明の化粧品組成物は、前記のような効果から、化粧品組成物や化粧品として利用されることは勿論であるが、その他にも、医薬部外品組成物、医療用品組成物、衛生用品組成物、医薬品組成物、機能性食品組成物や、医薬部外品、医療用品、衛生用品、医薬品などの形態やプレミックス品などの形態で利用することができる。 Of course, the cosmetic composition of the present invention can be used as a cosmetic composition or a cosmetic because of the above-mentioned effects. In addition, the quasi-drug composition, the medical product composition, and the hygiene product composition are used. Products, pharmaceutical compositions, functional food compositions, quasi-drugs, medical supplies, hygiene products, pharmaceutical products, and premixed products.
以下の実施例により、本発明を更に詳細に説明するが、本発明は、これらに何ら限定されるものではない。 The following examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.
(実施例1)
(1)L−PGAの製造
特許文献6(特開2007−314434号公報)に基づき得られ、かつ独立行政法人産業技術総合研究所特許生物寄託センタ−に寄託されているナトリアルバ エジプチアキア(Natrialba aegyptiaca)0831−264株 (受託番号:FERM BP−20874)のシングルコロニーを白金耳で1白金耳掻き取り、3mlのPGA生産液体培地−1(22.5% NaCl、2.0% MgSO4・7H2O、0.2% KCl、3.0% Trisodiumu Citrate、1.0% Yeast Extract、0.75% Cassamiono acid)/18ml容試験管×5本に植菌し、37℃ 300rpmで3日間培養した。得られた培養液0.5mlを 50mlのPGA生産液体培地−1/500ml容坂口フラスコ×10本に植菌し、37℃で5日間培養した。得られた培養液を遠心し、菌体を取り除いた。続いて、得られた上清液に3倍量の水を加え希釈した後、pHを3.0に調整した。pH調整後、5時間 室温で攪拌した。その後、3倍量のエタノ−ルを加え遠心分離を行い、ポリ−γ−L−グルタミン酸を沈殿物として回収した。沈殿物を0.1mM Tris−HCl緩衝液(pH8.0)に溶解させ、低分子物質を除去するために透析した。透析後、得られた液を核酸除去のため、1mM MgCl2 、10U/ml DNaseI(TaKaRa社製)、20μg/ml RNaseI(NIPPON GENE社製)となるように加え37℃で2時間インキュベ−トした。次いでタンパク質除去のために、3U/ml Proteinase K(TaKaRa社製)処理を37℃ 5時間インキュベ−トした。Proteinase K処理後、MilliQ水で透析し、低分子物質を除去した。透析後、ポリ−γ−L−グルタミン酸を陰イオン交換樹脂、Q sepharose Fast Flow(Amershama Biosciences社製)に吸着させ、洗浄後1M NaClで溶出した。得られた溶液をMilliQ水で透析し、透析後の溶液を凍結乾燥することにより、ポリ−γ−L−グルタミン酸・Na塩を得た。
得られたポリ−γ−L−グルタミン酸のH−NMRのスペクトル(500MHz)を重水を用いて測定し、ポリ−γ−L−グルタミン酸であることを確認した。
Example 1
(1) Production of L-PGA
Natalba aegyptica 0831-264 strain (Accession number :) obtained on the basis of Patent Document 6 (Japanese Patent Application Laid-Open No. 2007-314434) and deposited at the National Institute of Advanced Industrial Science and Technology Patent Biological Deposit Center A single colony of FERM BP-20874) was scraped with a platinum loop, and 3 ml of PGA production liquid medium-1 (22.5% NaCl, 2.0% MgSO 4 .7H 2 O, 0.2% KCl, 3 0% Trisodium Citrate, 1.0% Yeast Extract, 0.75% Cassiomino acid) / 18 ml test tube × 5 tubes, and cultured at 37 ° C. and 300 rpm for 3 days. 0.5 ml of the obtained culture solution was inoculated into 50 ml of PGA production liquid medium-1 / 500 ml Sakaguchi flask × 10 and cultured at 37 ° C. for 5 days. The obtained culture broth was centrifuged to remove the cells. Subsequently, the obtained supernatant was diluted with 3 times the amount of water, and then the pH was adjusted to 3.0. After pH adjustment, the mixture was stirred at room temperature for 5 hours. Thereafter, 3 times the amount of ethanol was added and centrifuged, and poly-γ-L-glutamic acid was recovered as a precipitate. The precipitate was dissolved in 0.1 mM Tris-HCl buffer (pH 8.0) and dialyzed to remove low molecular weight substances. After dialysis, the resulting solution was added to 1 mM MgCl 2 , 10 U / ml DNase I (TaKaRa), 20 μg / ml RNase I (NIPPON GENE) for incubation for 2 hours at 37 ° C. did. Subsequently, 3 U / ml Proteinase K (manufactured by TaKaRa) treatment was incubated at 37 ° C. for 5 hours for protein removal. After Proteinase K treatment, dialyzed against MilliQ water to remove low molecular weight substances. After dialysis, poly-γ-L-glutamic acid was adsorbed onto an anion exchange resin, Q Sepharose Fast Flow (manufactured by Amersham Biosciences), and after washing, eluted with 1M NaCl. The resulting solution was dialyzed against MilliQ water, and the solution after dialysis was freeze-dried to obtain poly-γ-L-glutamic acid / Na salt.
The H-NMR spectrum (500 MHz) of the obtained poly-γ-L-glutamic acid was measured using heavy water, and confirmed to be poly-γ-L-glutamic acid.
(2)Na塩のGPC分析及びIR分析
得られたポリ−γ−L−グルタミン酸・Na塩の平均分子量をGPC分析にて測定した。また、IR分析も行った。
GPC分析の結果、Mw=7,522,000、Mn=3,704,000、Mw/Mn=2.031、であることが確認された(プルラン換算)。
なお、前記GPCの分析条件は以下の通りである。
装置:HCl−8220GPC(東ソ−社製)
カラム:TSGel α−M(東ソ−社製)
流速:0.6ml/min
溶出液:0.15M NaCl水溶液
カラム温度:40℃
注入量:10μl
検出器:示差屈折計
IR分析の結果からNa塩であることが示された。
(2) GPC analysis and IR analysis of Na salt The average molecular weight of the obtained poly-γ-L-glutamic acid / Na salt was measured by GPC analysis. IR analysis was also performed.
As a result of GPC analysis, it was confirmed that Mw = 7,522,000, Mn = 3,704,000, and Mw / Mn = 2.031 (in pullulan conversion).
The GPC analysis conditions are as follows.
Apparatus: HCl-8220GPC (manufactured by Tosoh Corporation)
Column: TSGel α-M (manufactured by Tosoh Corporation)
Flow rate: 0.6 ml / min
Eluent: 0.15M NaCl aqueous solution Column temperature: 40 ° C
Injection volume: 10 μl
Detector: It was shown that it was Na salt from the result of the differential refractometer IR analysis.
(実施例2)L−PGA架橋体の製造
実施例1で得られたL−PGA・Na塩5重量%水溶液を作製、得られた5重量%L−PGA・Na塩水溶液を、窒素を用いて3分間バブリングした後、それぞれ2mlを、蓋付き10mlサンプル瓶に分取して蓋を閉めた。
(Example 2) Production of L-PGA cross-linked product A 5 wt% aqueous solution of L-PGA · Na salt obtained in Example 1 was prepared, and the obtained 5 wt% L-PGA · Na salt aqueous solution was used with nitrogen. After 3 minutes of bubbling, 2 ml of each was dispensed into 10 ml sample bottles with lids and the lids were closed.
次に、窒素を用いて3分間バブリングしたL−PGA・Na塩5重量%水溶液2mlを入れ蓋を閉めた該サンプル瓶に、線源をコバルト60とするγ線照射装置を用いてγ線を照射した。照射線量は、5kGyとなるように照射した。γ線照射後に得られた生成物を、サンプル瓶から取り出し、余分な水分を80メッシュの金網で水切りした後、凍結乾燥することで、L−PGA架橋体粉末を得た。なお、上記余分な水分には、未架橋のL−PGAが含まれており、当該水切りは、未架橋のL−PGAを除去することが主たる目的である。 Next, 2 ml of a 5% by weight aqueous solution of L-PGA / Na salt bubbled with nitrogen for 3 minutes was put in the sample bottle closed and γ-rays were emitted using a γ-ray irradiator with cobalt 60 as the radiation source. Irradiated. Irradiation dose was 5 kGy. The product obtained after γ-ray irradiation was taken out of the sample bottle, excess water was drained with an 80-mesh wire mesh, and freeze-dried to obtain L-PGA crosslinked powder. The excess water contains uncrosslinked L-PGA, and the main purpose of draining is to remove uncrosslinked L-PGA.
次に、得られたL−PGA架橋体粉末を、当該L−PGA架橋体粉末が膨潤するために十分な量の水に入れて1週間静置した。静置した後、80メッシュの金網で濾過することで、未架橋のL−PGAを除去して、ハイドロゲルを得た。 Next, the obtained L-PGA cross-linked powder was placed in a sufficient amount of water for the L-PGA cross-linked powder to swell and allowed to stand for 1 week. After leaving still, uncrosslinked L-PGA was removed by filtering with an 80 mesh wire mesh, and hydrogel was obtained.
(実施例3)美容液の製造
紫外線吸収剤を含むL−PGA架橋体美容液の製造
以下に示す組成の美容液を常法により製造した。L−PGA架橋体は実施例2に記載されているL−PGA架橋体を用いた。また、コントロール(比較例1)として、L−PGA架橋体を含まない美容液も常法により製造した。
(組成) (重量%)
油相成分:ステアリン酸 3.0
スクワラン 5.0
オリーブ油 5.0
ポリ−γ−L−グルタミン酸架橋体 2.0
乳化剤:POEソルビタンモノラウレート 5.0
ソルビタンモノステアレート 5.0
アルカリ:トリエタノールアミン 1.0
紫外線吸収剤:パラアミノ安息香酸オクチル 4.0
水相成分:プロピレングリコール 5.0
精製水 全体で100となる量
(Example 3) Manufacture of serum
Production of L-PGA crosslinked cosmetic liquid containing ultraviolet absorber A cosmetic liquid having the composition shown below was produced by a conventional method. As the L-PGA crosslinked product, the L-PGA crosslinked product described in Example 2 was used. Further, as a control (Comparative Example 1), a serum containing no crosslinked L-PGA was also produced by a conventional method.
(Composition) (wt%)
Oil phase component: stearic acid 3.0
Squalane 5.0
Olive oil 5.0
Poly-γ-L-glutamic acid crosslinked product 2.0
Emulsifier: POE sorbitan monolaurate 5.0
Sorbitan monostearate 5.0
Alkali: Triethanolamine 1.0
Ultraviolet absorber: Octyl paraaminobenzoate 4.0
Aqueous phase component: propylene glycol 5.0
Total amount of purified water is 100
(実施例4)紫外線吸収剤と抗菌剤を含むL−PGA架橋体美容液の製造
以下に示す組成の美容液を常法により製造した。L−PGA架橋体は実施例2に記載されているL−PGA架橋体塩を用いた。また、コントロール(比較例2)として、L−PGA架橋体を含まない美容液も常法により製造した。
(組成) (重量%)
油相成分:ステアリン酸 3.0
スクワラン 5.0
オリーブ油 5.0
ポリ−γ−L−グルタミン酸架橋体 2.0
乳化剤:POEソルビタンモノラウレート 5.0
ソルビタンモノステアレート 5.0
アルカリ:トリエタノールアミン 1.0
紫外線吸収剤:パラアミノ安息香酸オクチル 4.0
抗菌剤:ウンデシレン酸亜鉛 4.0
水相成分:プロピレングリコール 5.0
精製水 全体で100となる量
(Example 4) Manufacture of L-PGA crosslinked cosmetic liquid containing ultraviolet absorber and antibacterial agent A cosmetic liquid having the composition shown below was prepared by a conventional method. As the L-PGA crosslinked product, the L-PGA crosslinked salt described in Example 2 was used. In addition, as a control (Comparative Example 2), a serum containing no crosslinked L-PGA was also produced by a conventional method.
(Composition) (wt%)
Oil phase component: stearic acid 3.0
Squalane 5.0
Olive oil 5.0
Poly-γ-L-glutamic acid crosslinked product 2.0
Emulsifier: POE sorbitan monolaurate 5.0
Sorbitan monostearate 5.0
Alkali: Triethanolamine 1.0
Ultraviolet absorber: Octyl paraaminobenzoate 4.0
Antibacterial agent: zinc undecylenate 4.0
Aqueous phase component: propylene glycol 5.0
Total amount of purified water is 100
(実施例5)美容液の評価(対照区)
比較例1、比較例2の美容液を用いて、5名のパネリストが、これを使用したときの、のび、ヒリヒリ感のなさ、のび、ベタツキ感について評価し、次の基準に従って判定した。結果を表1に示す。判定基準:
◎:5名中4名以上が良好と評価した。
○:5名中3名が良好と評価した。
△:5名中2名が良好と評価した。
×:5名中1名以下が良好と評価した。
(Example 5) Evaluation of serum (control group)
Using the essence liquids of Comparative Examples 1 and 2, five panelists evaluated the spread, no tingling, spread and stickiness when using this, and judged according to the following criteria. The results are shown in Table 1. Judgment criteria:
A: 4 or more out of 5 evaluated as good.
A: 3 out of 5 people evaluated it as good.
(Triangle | delta): Two persons evaluated that 5 persons were favorable.
X: 1 or less out of 5 evaluated as good.
(実施例6)美容液の評価(L−PGA架橋体)
実施例3、実施例4に示した組成の美容液を用いて、5名のパネリストが、これを使用したときの、ヒリヒリ感のなさ、のび、ベタツキ感について評価し、次の基準に従って判定した。結果を表2に示す。なお、いずれの場合もL−PGA架橋体含有により、のび、しっとり感は良好で、刺激性の指標としたヒリヒリ感はなくなり、また、紫外線吸収効果の指標としてののび、ベタツキ感の効果も改善され全ての項目において良好と評価された。
判定基準:
◎:5名中4名以上が良好と評価した。
○:5名中3名が良好と評価した。
△:5名中2名が良好と評価した。
×:5名中1名以下が良好と評価した。
(Example 6) Evaluation of serum (L-PGA crosslinked product)
Using the serums of the compositions shown in Example 3 and Example 4, five panelists evaluated the absence of tingling, spread and stickiness when using this, and judged according to the following criteria: . The results are shown in Table 2. In any case, the presence of the L-PGA cross-linked product makes the spread and moist feeling good, eliminates the tingling sensation as an index of irritation, and improves the effect of spreading and stickiness as an index of the ultraviolet absorption effect. All items were evaluated as good.
Judgment criteria:
A: 4 or more out of 5 evaluated as good.
A: 3 out of 5 people evaluated it as good.
(Triangle | delta): Two persons evaluated that 5 persons were favorable.
X: 1 or less out of 5 evaluated as good.
本発明のL−PGA架橋体、並びに紫外線吸収剤を含有する化粧品組成物により、皮膚刺激性等の安全面に問題なく、さらにのびが良く、ベタツキ感が低減された化粧品、医薬部外品、医療用品、衛生用品、医薬品を提供することができる。さらに、従来より、原料コストが安価であり、大量生産可能となり、長期にわたる使用に十分に耐え得ることからも、産業界に大きく寄与することが期待される。 The cosmetic composition containing the L-PGA cross-linked product of the present invention and the ultraviolet absorber has no problem in safety such as skin irritation, and has a good spread and reduced stickiness, a quasi-drug, Medical supplies, hygiene supplies and medicines can be provided. Furthermore, since the raw material cost is low, mass production is possible, and it can sufficiently withstand long-term use, it is expected to contribute greatly to the industry.
Claims (5)
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