JP2006027917A - Silicon oligomer comprising sp2 hybrid orbital - Google Patents

Silicon oligomer comprising sp2 hybrid orbital Download PDF

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JP2006027917A
JP2006027917A JP2004204764A JP2004204764A JP2006027917A JP 2006027917 A JP2006027917 A JP 2006027917A JP 2004204764 A JP2004204764 A JP 2004204764A JP 2004204764 A JP2004204764 A JP 2004204764A JP 2006027917 A JP2006027917 A JP 2006027917A
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silicon oligomer
formula
oligomer
present
ultraviolet
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Masae Takahashi
まさえ 高橋
Yoshiyuki Kawazoe
良幸 川添
Yukimitsu Sumida
如光 隅田
Asa Kimura
朝 木村
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Tohoku University NUC
Shiseido Co Ltd
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Tohoku University NUC
Shiseido Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a new silicon oligomer having conductivity and ultraviolet absorbency. <P>SOLUTION: The silicon oligomer contains, as a constitutive unit, Si comprising SP2 hybrid orbital and has a structure in its molecule, which is expressed by formula (I):-(Si)<SB>n</SB>-N<, (wherein, n is an integer of ≥2). A conductive polymer and an ultraviolet absorbent, containing the oligomer, are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、新規なSP2混成軌道からなるシリコンオリゴマーに関し、更に詳しくは、導電性で、かつその一部は可視光を透過し、紫外線を選択的に吸収する新規なSP2混成軌道からなるシリコンオリゴマーに関する。   The present invention relates to a novel silicon oligomer comprising SP2 hybrid orbitals, and more particularly, a novel silicon oligomer comprising SP2 hybrid orbitals that are electrically conductive, part of which transmits visible light and selectively absorbs ultraviolet rays. About.

シリコンを含むオリゴマーとしてはシラアレンやシリレンなどが知られているが(非特許文献1参照)、これらは導電性を示さず、また紫外線吸収剤も有していない。一方、導電性ポリマーとしても特許文献1に、ポリピロール、ポリアニリン、ポリアセチレンなどが開示されている。   As oligomers containing silicon, silaallene, silylene and the like are known (see Non-Patent Document 1), but these do not exhibit conductivity and do not have an ultraviolet absorber. On the other hand, Patent Document 1 discloses polypyrrole, polyaniline, polyacetylene and the like as conductive polymers.

一方、紫外線はさまざまな変化を皮膚にもたらすことが知られている。皮膚科学的には作用波長を400〜320nmの長波長紫外線、320〜290nmの中波長紫外線及び290nm以下の短波長紫外線に分類し、それぞれ、UV−A,UV−B及びUV−Cと呼ばれている。通常、人間が暴露される紫外線の大部分は太陽光線であるが、地上に届く紫外線はUV−A及びUV−Bで、UV−Cはオゾン層において吸収されて地上には殆ど到達しない。地上まで到達する紫外線のなかで、UV−A及びUV−Bは、ある一定量以上の光量が皮膚に照射されると紅斑や水胞を形成し、またメラニンの形成が亢進され、色素沈着を生ずる等の変化をもたらす。従って、UV−A及びUV−Bから皮膚を保護することは、皮膚の老化促進を予防し、シミ、ソバカスの発生を防ぐ意味において極めて重要であり、かかる観点から、これまでに、種々のUV−A及びUV−B吸収剤が開発されてきた。既存のUV−A吸収剤としてはジベンゾイルメタン誘導体が知られている(例えば特許文献2参照)。一方、UV−B吸収剤としては、PABA誘導体、桂皮酸誘導体、サリチル酸誘導体、カンファー誘導体、ウロカニン酸誘導体、ベンゾフェノン誘導体及び複素環誘導体(特許文献3参照)が知られている。これらのUV−A及びUV−B吸収剤は、化粧料、医薬部外品等の皮膚外用剤に配合され、利用されている。   On the other hand, ultraviolet rays are known to cause various changes in the skin. In terms of dermatology, the working wavelengths are classified into long-wavelength ultraviolet rays of 400 to 320 nm, medium-wavelength ultraviolet rays of 320 to 290 nm and short-wavelength ultraviolet rays of 290 nm or less, which are called UV-A, UV-B and UV-C, respectively. ing. Usually, most of the ultraviolet rays to which humans are exposed is sunlight, but the ultraviolet rays that reach the ground are UV-A and UV-B, and UV-C is absorbed in the ozone layer and hardly reaches the ground. Among the ultraviolet rays reaching the ground, UV-A and UV-B form erythema and vesicles when the skin is irradiated with a certain amount of light, and melanin formation is enhanced, causing pigmentation. It brings about changes that occur. Therefore, protecting the skin from UV-A and UV-B is extremely important in terms of preventing the promotion of skin aging and preventing the occurrence of spots and freckles. -A and UV-B absorbers have been developed. A dibenzoylmethane derivative is known as an existing UV-A absorber (see, for example, Patent Document 2). On the other hand, PABA derivatives, cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, urocanic acid derivatives, benzophenone derivatives, and heterocyclic derivatives (see Patent Document 3) are known as UV-B absorbers. These UV-A and UV-B absorbers are blended and used in skin external preparations such as cosmetics and quasi drugs.

Chemical Reviews 2000,100,3639−3696Chemical Reviews 2000, 100, 3639-3696 特開平5−36999号公報JP-A-5-36999 特開平5−247063号公報Japanese Patent Laid-Open No. 5-247063 特開2003−212711号公報JP 2003-2112711 A

従って、本発明の目的は、導電性を示し、またUV−A及び/又はUV−B領域の波長を選択的に吸収すると共に、可視光領域に実質的な吸収を有しないシリコンオリゴマーを提供することにある。   Accordingly, it is an object of the present invention to provide a silicon oligomer that exhibits electrical conductivity, selectively absorbs wavelengths in the UV-A and / or UV-B region, and has no substantial absorption in the visible region. There is.

本発明に従えば、SP2混成軌道からなるSiを構成単位として含み、そして式(I):
−(Si)n−N< (I)
(式中、nは2以上の整数を示す)
で表される構造を分子中に含むシリコンオリゴマーが提供される。
According to the present invention, Si comprising SP2 hybrid orbitals is included as a structural unit, and the formula (I):
-(Si) n- N <(I)
(In the formula, n represents an integer of 2 or more)
A silicon oligomer containing a structure represented by the formula:

本発明に従えば、また、前記式(I)で表わされる構造を含む導電性ポリマーが提供される。   According to the present invention, there is also provided a conductive polymer comprising the structure represented by the formula (I).

本発明に従えば、更に、式(I)の構造においてn=2〜5の少なくとも一種のシリコンオリゴマーを含んでなる紫外線吸収剤及びそれを含む皮膚外用剤が提供される。   According to the present invention, there are further provided an ultraviolet absorber comprising at least one silicon oligomer of n = 2 to 5 in the structure of formula (I) and a skin external preparation comprising the same.

本発明に係るシリコンオリゴマーは、新規であり、そしてSiがSP2混成軌道にて結合していること、オリゴマー分子の一方又は両方の末端SiにNが結合しており、一つの末端Siに結合しているN原子の数が1個のみ即ち、Si−(NR22ではなく、Si−NR2であること(式中、Rは例えばH又はメチル、フェニルなどの炭化水素基を示す)により、導電性を示し、そしてオリゴマー分子中のSiの数が2〜5個の場合にはUV−A及び/又はUV−B波長領域を吸収し、UV−A及び/又はUV−B領域の波長を十分に吸収防御すると同時に、可視光領域に実質的に吸収を有さないので紫外線吸収剤及びそれを配合した皮膚外用剤として有用である。 The silicon oligomer according to the present invention is novel, and Si is bonded by SP2 hybrid orbitals, N is bonded to one or both terminal Si of the oligomer molecule, and is bonded to one terminal Si. The number of N atoms contained is only one, ie, Si—NR 2 , not Si— (NR 2 ) 2 (wherein R represents a hydrocarbon group such as H or methyl, phenyl, etc.) In the case where the number of Si in the oligomer molecule is 2 to 5, it absorbs the UV-A and / or UV-B wavelength region, and the wavelength in the UV-A and / or UV-B region. Is sufficiently absorbed and protected, and has substantially no absorption in the visible light region, so that it is useful as an ultraviolet absorber and a skin external preparation containing the same.

即ち、本発明者らは、SP2混成軌道からなるSiを構造単位として含むシリコン化合物の開発を進めている過程で、前記式(I)の構造を分子内に有するシリコンオリゴマーを見出し、しかもそのオリゴマーが導電性を有し、かつ式(I)のnが2〜5のオリゴマーは可視光を実質的に吸収することなく、UV−A及び/又はUV−B波長領域に適切な吸収能を有することを見出した。即ち、本発明のオリゴマーは導電性ポリマーとして有用であり、また一部は紫外線吸収剤としても極めて有用な物質である。   That is, the present inventors have found a silicon oligomer having a structure of the above formula (I) in the molecule in the process of developing a silicon compound containing Si as a structural unit composed of SP2 hybrid orbitals. Are conductive and the oligomer of formula (I) n = 2 to 5 does not substantially absorb visible light, and has an appropriate absorption capacity in the UV-A and / or UV-B wavelength region. I found out. That is, the oligomer of the present invention is useful as a conductive polymer, and a part thereof is a very useful substance as an ultraviolet absorber.

本発明に係るシリコンオリゴマーは導電性を示し、必要に応じ一般的な添加剤を配合して、導電性フィルム、半導体、光学材料、燃料電池などの導電性ポリマーとして使用することができる。また本発明の式(I)のシリコンオリゴマーはn=2〜5の場合に、紫外線領域を選択的に吸収することができ、しかも400〜700nmの可視光領域では殆んど吸収を示さず、400nm以下の紫外線領域で顕著な吸収ピークを示している。このことは、従来の無機紫外線防御剤のようなバルク化合物(例えば酸化チタン、酸化亜鉛、酸化セレン)ではなし得ない効果であり、本発明のようなSP2混成軌道からなるSiを構成単位として含み、しかもオリゴマーの両末端Siの少なくとも一方にN原子を1個のみ有するシリコンオリゴマーであるからこそなし得た効果である。本発明のシリコンオリゴマーは、目的とする紫外線領域のみを吸収して、透明性と紫外線吸収性とを両立させることができるので、特に商品形態上、審美性、透明性が重要な化粧料、医薬部外品、その他の皮膚外用剤用の紫外線吸収剤として使用するのに好適である。   The silicon oligomer according to the present invention exhibits electrical conductivity, and can be used as a conductive polymer for conductive films, semiconductors, optical materials, fuel cells, etc. by blending general additives as necessary. The silicon oligomer of the formula (I) of the present invention can selectively absorb the ultraviolet region when n = 2 to 5, and shows little absorption in the visible light region of 400 to 700 nm. A remarkable absorption peak is shown in the ultraviolet region of 400 nm or less. This is an effect that cannot be achieved with a bulk compound (eg, titanium oxide, zinc oxide, selenium oxide) such as a conventional inorganic ultraviolet protective agent, and contains Si composed of SP2 hybrid orbital as in the present invention. Moreover, this is an effect that can be achieved because it is a silicon oligomer having only one N atom in at least one of both ends Si of the oligomer. Since the silicon oligomer of the present invention can absorb only the target ultraviolet region and achieve both transparency and ultraviolet absorption, cosmetics and pharmaceuticals in which aesthetics and transparency are particularly important in terms of product form It is suitable for use as an ultraviolet absorber for quasi-drugs and other skin external preparations.

本発明に従ったシリコンオリゴマーは前記式(I)の構造を分子中に有するものであり、式(I)において、nは2以上を示す。   The silicon oligomer according to the present invention has the structure of the above formula (I) in the molecule, and in the formula (I), n represents 2 or more.

前記SP2混成軌道からなるSiを構成単位として含み、そして式(I)の構造を分子中に有するシリコンオリゴマーは、例えばかさ高い置換基を有するSiNR12(R1及びR2は、それぞれ独立に、例えば、2,4,6−t−ブチルフェニル基、1144−テトラキスフェニルブチル基、NN’ビストリメチルシリルエチレンジアミンなど)を、必要であれば反応助剤(例えば炭化カリウムなど)の存在下にて、THF中で還流することによって製造することができる。 The silicon oligomer containing Si composed of the SP2 hybrid orbital as a structural unit and having the structure of formula (I) in the molecule is, for example, SiNR 1 R 2 having a bulky substituent (R 1 and R 2 are each independently In addition, for example, 2,4,6-t-butylphenyl group, 1144-tetrakisphenylbutyl group, NN′bistrimethylsilylethylenediamine, etc.) may be added in the presence of a reaction aid (eg, potassium carbide) if necessary. Can be prepared by refluxing in THF.

本発明の皮膚外用剤は、特にその適用分野を限定するものではなく、本発明に用いるシリコンオリゴマーの特性と目的に応じ、化粧料、頭髪用化粧料、医薬部外品等の分野で利用することができる。   The topical skin preparation of the present invention is not particularly limited in the field of application, and is used in the fields of cosmetics, hair cosmetics, quasi drugs, etc. according to the characteristics and purpose of the silicon oligomer used in the present invention. be able to.

本発明の皮膚外用剤の剤型は任意であり、例えばパウダー状、クリーム状、ペースト状、スチック状、液状、スプレー状、ファンデーション等のいずれの剤型でもかまわず、また、乳化剤を用いてW/O型及びO/W型に乳化して使用しても良い。   The dosage form of the external preparation for skin of the present invention is arbitrary, and any dosage form such as powder, cream, paste, stick, liquid, spray, foundation, etc. may be used. / O type and O / W type may be used after emulsification.

本発明に係る式(I)の構造において、nは2〜5のシリコンオリゴマーは、特にその適用分野を限定するものではなく、紫外線吸収剤が利用される各種製品に紫外線吸収有効量で利用することができる。特に、化粧料、医薬部外品等の皮膚外用剤に配合する場合の配合量は、その剤型によっても異なるが、所望の効果を得るためには、一般には皮膚外用剤重量の0.1〜20重量%、好ましくは0.5〜10重量%である。   In the structure of the formula (I) according to the present invention, n is a silicon oligomer having 2 to 5 in particular, and does not limit the application field, and is used in various products in which an ultraviolet absorber is used in an ultraviolet absorption effective amount. be able to. In particular, the amount to be blended in a skin external preparation such as cosmetics and quasi-drugs varies depending on the dosage form, but in order to obtain a desired effect, the weight of the skin external preparation is generally 0.1%. -20% by weight, preferably 0.5-10% by weight.

以下に本発明の実施例を示して本発明を更に詳しく説明するが、本発明をこれらの実施例に限定するものでないことはいうまでもない。
本発明に係る式(I)のシリコンオリゴマーの合成例及びその物理化学的性質並びに配合例を以下に説明する。
EXAMPLES The present invention will be described in more detail below with reference to examples of the present invention, but it goes without saying that the present invention is not limited to these examples.
Synthesis examples of the silicon oligomer of the formula (I) according to the present invention, physicochemical properties and blending examples thereof will be described below.

実施例1
以下に本発明のシリコンオリゴマーSi4(NH22は以下のようにして合成する。
SiNH21g、炭化カリウム3gをTHF100ml中に加え、−40℃にて12時間攪拌すると、Si4(NH22が得られる。本物質の吸収スペクトルを図1に示す。
Example 1
Hereinafter, the silicon oligomer Si 4 (NH 2 ) 2 of the present invention is synthesized as follows.
When 1 g of SiNH 2 and 3 g of potassium carbide are added to 100 ml of THF and stirred at −40 ° C. for 12 hours, Si 4 (NH 2 ) 2 is obtained. The absorption spectrum of this substance is shown in FIG.

実施例2
本発明のシリコンオリゴマーHSi6NH2は以下のようにして合成する。
実施例1にて得られるSi4(NH221gとSiCl45gをTHF100mlに加え24時間攪拌し、さらにLiH0.2gを加えるとHSi6NH2が得られる。本物質の吸収スペクトルを図2に示す。
Example 2
The silicon oligomer HSi 6 NH 2 of the present invention is synthesized as follows.
1 g of Si 4 (NH 2 ) 2 obtained in Example 1 and 5 g of SiCl 4 are added to 100 ml of THF and stirred for 24 hours. When 0.2 g of LiH is further added, HSi 6 NH 2 is obtained. The absorption spectrum of this substance is shown in FIG.

紫外線吸収能という観点から本物質を評価すると、図1(Si4)では紫外線領域に優れた吸収能を示すが、図2(Si6)では吸収が可視光領域にシフトする。従って紫外線吸収剤としては、式I中のnが2〜5であるのが好適である。 When this substance is evaluated from the viewpoint of ultraviolet absorbing ability, FIG. 1 (Si 4 ) shows an excellent absorbing ability in the ultraviolet region, but in FIG. 2 (Si 6 ), the absorption shifts to the visible light region. Accordingly, as the ultraviolet absorber, n in the formula I is preferably 2 to 5.

次に本発明に係るシリコンオリゴマーの紫外線吸収剤としての配合実施例を示す。なお、図1に示した通りシリコンオリゴマーのUVスペクトルから、本発明の紫外線吸収剤は、特にUV−A(400〜320nm)及び/又はUV−B(320〜290nm)吸収能に優れ、紫外線吸収効果を有することがわかる。   Next, blending examples of the silicon oligomer according to the present invention as an ultraviolet absorber will be shown. As shown in FIG. 1, from the UV spectrum of the silicon oligomer, the ultraviolet absorber of the present invention is particularly excellent in UV-A (400 to 320 nm) and / or UV-B (320 to 290 nm) absorption, and absorbs ultraviolet rays. It turns out that it has an effect.

実施例3:紫外線吸収剤の配合例(油状タイプ)
配合成分 配合量(重量%)
(1)デカメチルシクロペンタシロキサン 48.0
(2)ジメチルポリシロキサン(10cs/25℃) 20.0
(3)メチルフェニルポリシロキサン(20cs/25℃) 20.0
(4)シリコーン樹脂 10.0
(5)シリコンオリゴマー(実施例1) 2.0
これらを混合し、十分に溶解した後、濾過して製品とする。
Example 3: Formulation of UV absorber (oil type)
Compounding ingredients blending amount (% by weight)
(1) Decamethylcyclopentasiloxane 48.0
(2) Dimethylpolysiloxane (10 cs / 25 ° C.) 20.0
(3) Methylphenylpolysiloxane (20 cs / 25 ° C.) 20.0
(4) Silicone resin 10.0
(5) Silicon oligomer (Example 1) 2.0
These are mixed and sufficiently dissolved, and then filtered to obtain a product.

比較例1
上記実施例3の配合例の処方中、成分(5)を除く以外は実施例3と同様にして皮膚外用剤を得る。
Comparative Example 1
An external preparation for skin is obtained in the same manner as in Example 3 except that the component (5) is excluded during the formulation of the formulation example of Example 3 above.

以上のようにして得られた実施例3及び比較例1について紫外線防止効果の測定を行う。紫外線防止効果の測定は、特開昭62−112020号公報に記載の紫外線感受性組成物を用いて行う。実施例3の配合の色差は対応する比較例1の色差より小さく、紫外線防止効果が高くなっている。このようにして、本発明の紫外線吸収剤を配合することにより優れた紫外線防止効果が得られることが確認される。   With respect to Example 3 and Comparative Example 1 obtained as described above, the effect of preventing ultraviolet rays is measured. The measurement of the effect of preventing ultraviolet rays is performed using an ultraviolet sensitive composition described in JP-A-62-112020. The color difference of the composition of Example 3 is smaller than the color difference of the corresponding Comparative Example 1, and the effect of preventing ultraviolet rays is high. In this way, it is confirmed that an excellent ultraviolet ray preventing effect can be obtained by blending the ultraviolet absorbent according to the present invention.

以下に皮膚外用剤の他の実施例(配合例)を示す。
実施例4:日焼け止め化粧料(油状タイプ)
配合成分 配合量(重量%)
(1)デカメチルシクロペンタシロキサン 48.0
(2)ジメチルポリシロキサン(10CS/25℃) 20.0
(3)メチルフェニルポリシロキサン(20CS/25℃) 20.0
(4)シリコーン樹脂 10.0
(5)シリコンオリゴマー(実施例1) 2.0
Other examples (formulation examples) of the external preparation for skin are shown below.
Example 4: Sunscreen cosmetic (oil type)
Compounding ingredients blending amount (wt%)
(1) Decamethylcyclopentasiloxane 48.0
(2) Dimethylpolysiloxane (10 CS / 25 ° C.) 20.0
(3) Methylphenylpolysiloxane (20 CS / 25 ° C.) 20.0
(4) Silicone resin 10.0
(5) Silicon oligomer (Example 1) 2.0

(製法)成分(1)〜(5)を混合し、十分に溶解した後、濾過して製品とした。   (Production method) Components (1) to (5) were mixed and sufficiently dissolved, and then filtered to obtain a product.

実施例5:日焼け止め化粧料(W/Oクリーム)
配合成分 配合量(重量%)
(1)オクタメチルシクロテトラシロキサン 28.0
(2)ジメチルポリシロキサン(100CS/25℃) 5.0
(3)ジメチルポリシロキサン(2,500,000CS/25℃) 3.0
(4)流動パラフィン 5.0
(5)シリコンオリゴマー(実施例1) 1.5
(6)ポリエーテル変性シリコーン(400CS/25℃)
(ポリオキシエチレン基含量 20重量%) 6.0
(7)精製水 43.1
(8)L−グルタミン酸ナトリウム 3.0
(9)1,3−ブチレングリコール 5.0
(10)防腐剤 0.2
(11)香料 0.2
Example 5: Sunscreen cosmetic (W / O cream)
Compounding ingredients blending amount (% by weight)
(1) Octamethylcyclotetrasiloxane 28.0
(2) Dimethylpolysiloxane (100 CS / 25 ° C.) 5.0
(3) Dimethylpolysiloxane (2,500,000 CS / 25 ° C.) 3.0
(4) Liquid paraffin 5.0
(5) Silicon oligomer (Example 1) 1.5
(6) Polyether-modified silicone (400CS / 25 ° C)
(Polyoxyethylene group content 20% by weight) 6.0
(7) Purified water 43.1
(8) Sodium L-glutamate 3.0
(9) 1,3-butylene glycol 5.0
(10) Preservative 0.2
(11) Fragrance 0.2

(製法)成分(1)〜(6)及び(11)を混合し、加熱溶解して70℃に保ち油相部とし、別に成分(7)〜(10)を加熱溶解して70℃に保ち水相部とした。この油相部に水相部を添加して乳化機により十分に乳化した。乳化後、撹拌しながら冷却し、35℃以下になったら容器に流し込み放冷して固めた。   (Manufacturing method) Components (1) to (6) and (11) are mixed, dissolved by heating and kept at 70 ° C. to form an oil phase part, and separately components (7) to (10) are heated and dissolved and kept at 70 ° C. The aqueous phase was used. The water phase part was added to this oil phase part, and it fully emulsified with the emulsifier. After emulsification, the mixture was cooled with stirring, and when it became 35 ° C. or lower, it was poured into a container and allowed to cool to be hardened.

実施例6:日焼け止め化粧料(O/Wクリーム)
配合成分 配合量(重量%)
(1)デカメチルシクロペンタシロキサン 9.0
(2)流動パラフィン 3.0
(3)イソプロピルミリステート 2.0
(4)ワセリン 5.0
(5)セタノール 5.0
(6)ステアリン酸 3.0
(7)グリセリルモノイソステアレート 3.0
(8)シリコンオリゴマー(実施例1) 1.0
(9)防腐剤 0.2
(10)香料 0.2
(11)グリセリン 10.0
(12)プロピレングリコール 5.0
(13)ヒアルロン酸 0.01
(14)水酸化カリウム 0.2
(15)精製水 53.39
Example 6: Sunscreen cosmetic (O / W cream)
Compounding ingredients blending amount (wt%)
(1) Decamethylcyclopentasiloxane 9.0
(2) Liquid paraffin 3.0
(3) Isopropyl myristate 2.0
(4) Vaseline 5.0
(5) Cetanol 5.0
(6) Stearic acid 3.0
(7) Glyceryl monoisostearate 3.0
(8) Silicon oligomer (Example 1) 1.0
(9) Preservative 0.2
(10) Fragrance 0.2
(11) Glycerin 10.0
(12) Propylene glycol 5.0
(13) Hyaluronic acid 0.01
(14) Potassium hydroxide 0.2
(15) Purified water 53.39

(製法)成分(1)〜(10)を70℃で加熱攪拌して油相部とし、成分(11)〜(15)を70℃に加熱し完全溶解した後水相部とする。油相部を水相部に添加し乳化機にて乳化し、得られた乳化物を熱交換器にて30℃まで冷却し、容器に充填して製品を得る。   (Manufacturing method) Components (1) to (10) are heated and stirred at 70 ° C. to obtain an oil phase part, and components (11) to (15) are heated to 70 ° C. and completely dissolved to obtain an aqueous phase part. The oil phase part is added to the water phase part and emulsified with an emulsifier, and the resulting emulsion is cooled to 30 ° C. with a heat exchanger and filled into a container to obtain a product.

実施例7:日焼け止めローション
配合成分 配合量(重量%)
(1)ジメチルポリシロキサン(5CS/25℃) 10.0
(2)メチルフェニルポリシロキサン(20CS/25℃) 7.0
(3)ステアリン酸 1.0
(4)シリコンオリゴマー(実施例1) 10.0
(5)防腐剤 0.2
(6)香料 0.2
(7)グリセリン 5.0
(8)モンモリロナイト 0.5
(9)水酸化カリウム 0.2
(10)精製水 65.9
Example 7: Sunscreen lotion
Compounding ingredients blending amount (wt%)
(1) Dimethylpolysiloxane (5CS / 25 ° C) 10.0
(2) Methylphenylpolysiloxane (20 CS / 25 ° C.) 7.0
(3) Stearic acid 1.0
(4) Silicon oligomer (Example 1) 10.0
(5) Preservative 0.2
(6) Fragrance 0.2
(7) Glycerin 5.0
(8) Montmorillonite 0.5
(9) Potassium hydroxide 0.2
(10) Purified water 65.9

(製法)成分(1)〜(6)を70℃で加熱攪拌して油相部とし、成分(7)〜(10)を70℃に加熱溶解し水相部とした。次に油相部を水相部中に添加し、乳化機にて乳化し、得られた乳化物を熱交換器にて30℃まで冷却した後、充填し日焼け止めローションを得た。   (Production Method) Components (1) to (6) were heated and stirred at 70 ° C. to obtain an oil phase part, and components (7) to (10) were heated and dissolved at 70 ° C. to obtain an aqueous phase part. Next, the oil phase portion was added to the water phase portion, emulsified with an emulsifier, and the obtained emulsion was cooled to 30 ° C. with a heat exchanger and then filled to obtain a sunscreen lotion.

本発明に係る、SP2混成軌道からなるSiを構成単位として含み、そして式(I)の構成を含むシリコンオリゴマーは、導電性に優れているので導電性フィルム、半導体、光学材料、燃料電池などの導電性ポリマーとして有用であり、そして式(I)においてn=2〜5のシリコンオリゴマーは、UV−A及び/又はUV−B領域の波長を十分に吸収防御すると同時に、可視光領域に実質的な吸収を有さず、皮膚外用剤中に、紫外線吸収剤として、目的に応じた任意の量で配合することができる。   According to the present invention, since the silicon oligomer containing Si composed of SP2 hybrid orbits and containing the structure of formula (I) is excellent in conductivity, such as conductive film, semiconductor, optical material, fuel cell, etc. Silicon oligomers that are useful as conductive polymers and in formula (I), where n = 2 to 5 sufficiently absorb and protect wavelengths in the UV-A and / or UV-B regions, while being substantially in the visible region. Therefore, it can be blended in the external preparation for skin as an ultraviolet absorber in any amount depending on the purpose.

実施例1の本発明に係るシリコンオリゴマーの吸収スペクトルを示す。The absorption spectrum of the silicon oligomer which concerns on this invention of Example 1 is shown. 実施例2の本発明のシリコンオリゴマーの吸収スペクトルを示す。The absorption spectrum of the silicon oligomer of this invention of Example 2 is shown.

Claims (4)

SP2混成軌道からなるSiを構成単位として含み、そして式(I):
−(Si)n−N< (I)
(式中、nは2以上の整数を示す)
で表される構造を分子中に含むシリコンオリゴマー。
It contains Si consisting of SP2 hybrid orbital as a structural unit and has the formula (I):
-(Si) n- N <(I)
(In the formula, n represents an integer of 2 or more)
Silicon oligomer containing in the molecule the structure represented by
請求項1に記載の式(I)の構造を含んでなる導電性ポリマー。   A conductive polymer comprising the structure of formula (I) according to claim 1. 請求項1に記載の式(I)においてnが2〜5の少なくとも一種のシリコンオリゴマーを含んでなる紫外線吸収剤。   An ultraviolet absorber comprising at least one silicon oligomer in which n is 2 to 5 in formula (I) according to claim 1. 請求項3に記載の紫外線吸収剤を配合してなる皮膚外用剤。   A skin external preparation comprising the ultraviolet absorbent according to claim 3.
JP2004204764A 2004-07-12 2004-07-12 Silicon oligomer comprising sp2 hybrid orbital Pending JP2006027917A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009137902A (en) * 2007-12-07 2009-06-25 Kao Corp Ultraviolet protective agent and sunscreen cosmetic
WO2012128131A1 (en) 2011-03-23 2012-09-27 株式会社Ihi Ultraviolet absorbent and cosmetic preparation using same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63234033A (en) * 1987-03-23 1988-09-29 Nippon Telegr & Teleph Corp <Ntt> Organometallic polymer
JPH0363284A (en) * 1989-08-01 1991-03-19 Mitsui Petrochem Ind Ltd Production of silazanes
JPH07242830A (en) * 1994-03-08 1995-09-19 Shin Etsu Chem Co Ltd Electroconducting polymer composition
JPH08337440A (en) * 1995-06-08 1996-12-24 Mitsubishi Chem Corp Production of polyorganosilane film
JP2003212711A (en) * 2002-01-24 2003-07-30 Shiseido Co Ltd Make-up cosmetic

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63234033A (en) * 1987-03-23 1988-09-29 Nippon Telegr & Teleph Corp <Ntt> Organometallic polymer
JPH0363284A (en) * 1989-08-01 1991-03-19 Mitsui Petrochem Ind Ltd Production of silazanes
JPH07242830A (en) * 1994-03-08 1995-09-19 Shin Etsu Chem Co Ltd Electroconducting polymer composition
JPH08337440A (en) * 1995-06-08 1996-12-24 Mitsubishi Chem Corp Production of polyorganosilane film
JP2003212711A (en) * 2002-01-24 2003-07-30 Shiseido Co Ltd Make-up cosmetic

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Title
JPN7010004165, Masae Takahashi and Yoshiyuki Kawazoe, "Theoretical Study on Planar Anionic Polysilicon Chains and Cyclic Si6 Anions with D6h Symmetry", Organometallics, 2005, Vol.24 No.10, p.2433−2440 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009137902A (en) * 2007-12-07 2009-06-25 Kao Corp Ultraviolet protective agent and sunscreen cosmetic
WO2012128131A1 (en) 2011-03-23 2012-09-27 株式会社Ihi Ultraviolet absorbent and cosmetic preparation using same

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