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JP2007191434A - Hair growth/hair-fostering cosmetic - Google Patents

Hair growth/hair-fostering cosmetic Download PDF

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JP2007191434A
JP2007191434A JP2006011541A JP2006011541A JP2007191434A JP 2007191434 A JP2007191434 A JP 2007191434A JP 2006011541 A JP2006011541 A JP 2006011541A JP 2006011541 A JP2006011541 A JP 2006011541A JP 2007191434 A JP2007191434 A JP 2007191434A
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hair
extract
growth
integer
isopolyacid
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Katsuaki Dan
克昭 団
Toshihiro Yamase
利博 山瀬
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Keio University
Tokyo Institute of Technology NUC
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Keio University
Tokyo Institute of Technology NUC
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair growth/hair-fostering cosmetic which is cheap and exhibits large effect. <P>SOLUTION: The hair growth/hair-fostering cosmetic contains an isopolyacid or heteropolyacid containing tungsten ion (W<SP>6+</SP>) and/or molybdenum ion (Mo<SP>6+</SP>). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、育毛、養毛及び脱毛防止作用を有する養毛・育毛料に関する。詳しくは、毛母細胞と毛乳頭細胞との相互作用を増強し、毛母細胞の増殖を活性化することにより、毛の成長促進、抜毛防止効果等の優れた特性を有する養毛・育毛料に関する。   The present invention relates to a hair nourishing and hair restoring material having an effect of hair growth, hair nourishing and hair loss prevention. Specifically, the hair nourishing and hair restorer has excellent properties such as hair growth promotion and hair removal prevention effect by enhancing the interaction between hair matrix cells and hair papilla cells and activating proliferation of hair matrix cells. About.

毛は成長期、退行期、休止期の毛周期をもって成長している。毛が成長する期間、毛包は成長期にあると言われ、その後、退行期を経て毛の成長が停止し、成長期よりも萎縮した状態の毛包を有するとき、毛包は休止期にあると言われる。この毛周期の障害は脱毛症を引き起こす。例えば、ヒトにおいて最も普通の脱毛症である男性型脱毛症は、毛包の数の減少ではなく、繰り返される毛周期において、成長期間が短縮したために硬毛がその大きさを漸次的に縮小化することに起因している。   The hair grows with a hair cycle of a growth phase, a regression phase, and a resting phase. During the period of hair growth, the hair follicle is said to be in the growth phase, after which it stops growing through the regression phase and has a hair follicle that is more atrophied than the growth phase, and the hair follicle is in the resting phase. It is said that there is. This hair cycle disorder causes alopecia. For example, androgenetic alopecia, the most common alopecia in humans, is not a reduction in the number of hair follicles, but with repeated hair cycles, the bristles gradually shrink their size due to shortened growth periods Is due to

ヒト毛髪毛包は、角化細胞、毛乳頭細胞、繊維芽細胞、脂腺細胞等の様々な上皮系細胞及び真皮間様系細胞から構成されており、これらの細胞間相互作用を介して、毛周期が調節されている。毛の本体は、毛包角化細胞の増殖/分化(角化)により形成されるが、この毛包角化細胞の増殖、分化及びアポトーシスを制御し、毛周期調節の中心的な役割を担っているのは、毛乳頭である。従って、発毛剤や育毛剤を開発する上で毛乳頭細胞に対する作用を研究することは重要である。毛母細胞と毛乳頭細胞との相互作用を増強し、毛母細胞の増殖を活性化することにより、毛の成長促進、抜毛防止効果等を有する育毛促進剤として、例えば、特許文献1〜3が知られている。   Human hair follicles are composed of various epithelial cells such as keratinocytes, dermal papilla cells, fibroblasts, and sebaceous cells, and dermal-like cells, and through these cell-cell interactions, The cycle is adjusted. The hair body is formed by the proliferation / differentiation (keratinization) of hair follicle keratinocytes, and controls the growth, differentiation and apoptosis of the hair follicle keratinocytes and plays a central role in the regulation of the hair cycle. It is the hair papilla. Therefore, it is important to study the effect on hair papilla cells in developing hair growth agents and hair growth agents. For example, Patent Documents 1 to 3 can be used as hair growth promoters that enhance the interaction between hair matrix cells and dermal papilla cells and activate the growth of hair matrix cells, thereby promoting hair growth and preventing hair removal. It has been known.

一方、本発明者等は、ポリ酸の無機医薬への応用を長年に渡って研究している。具体的には、本発明者等は、ポリ酸の、各種抗ウイルス剤、抗癌剤としての非常に有効な生理活性を報告している(例えば、非特許文献1参照)。
特開平08−012530号公報 特開平09−012432号公報 特開2005−041871号公報 T. Yamase Journal of Materials Chemistry, 2005, 15, 4773-4782
On the other hand, the present inventors have been studying the application of polyacids to inorganic medicines for many years. Specifically, the present inventors have reported very effective physiological activities of polyacids as various antiviral agents and anticancer agents (see, for example, Non-Patent Document 1).
Japanese Patent Laid-Open No. 08-012530 JP 09-012432 A JP 2005-041871 A T. Yamase Journal of Materials Chemistry, 2005, 15, 4773-4782

毛は休止期から成長期に入る時期において、新しい毛包を形成するために毛母細胞と毛乳頭細胞との相互作用を強め、毛母細胞の増殖を誘導化し、更に活性化する。よって、毛周期の障害による脱毛症に見られる縮小化した毛包を拡大するためには、生体内において毛母細胞と毛乳頭細胞との相互作用を増強し、毛母細胞の増殖を促進する物質が求められている。
しかしながら、特許文献1に記載の育毛促進剤は、表皮細胞を毛母細胞に変える毛乳頭細胞ではなく、毛母細胞自体の増殖を直接活性化するものであり、また熱処理に対して不安定である。更に、特許文献3では、「毛乳頭細胞増殖促進効果」が記載されているのみであり、特許文献2では、「毛乳頭細胞増殖促進効果」に加えて「毛幹伸長に及ぼす効果」についても記載されているものの、その効果は十分ではない。
従って、本発明の目的は、安価でより大きな効果を示す養毛・育毛料を提供することにある。
When the hair enters the growth phase from the resting phase, the interaction between the hair matrix cells and the hair papilla cells is strengthened to form new hair follicles, and the proliferation of the hair matrix cells is induced and further activated. Therefore, in order to expand the reduced hair follicles seen in alopecia due to hair cycle disorder, the interaction between hair matrix cells and hair papilla cells is enhanced in vivo, and the growth of hair matrix cells is promoted Substances are sought.
However, the hair growth-promoting agent described in Patent Document 1 directly activates the growth of hair matrix cells, not the hair papilla cells that change epidermal cells into hair matrix cells, and is unstable to heat treatment. is there. Further, Patent Document 3 only describes “papillary cell proliferation promoting effect”, and Patent Document 2 describes “effect on hair shaft elongation” in addition to “hair papillary cell proliferation promoting effect”. Although described, the effect is not sufficient.
Accordingly, an object of the present invention is to provide a hair nourishing and hair restorer that is inexpensive and exhibits a greater effect.

本発明者らは、斯かる実情に鑑み鋭意検討したところ、驚くべきことに、ポリ酸が毛乳頭細胞増殖活性を有し、その結果、毛の成長を促進することを見出し、本発明を完成させた。
すなわち、本発明は、タングステンイオン(W6+)及び/又はモリブテンイオン(Mo6+)を含有するイソポリ酸又はヘテロポリ酸を含む、養毛・育毛料を提供する。
The present inventors have intensively studied in view of such circumstances, and surprisingly found that the polyacid has hair papillary cell proliferation activity and, as a result, promotes hair growth, thereby completing the present invention. I let you.
That is, the present invention includes an isopoly acid or heteropoly acid-containing tungsten ions (W 6+) and / or molybdenum ions (Mo 6+), provides a hair grower fee.

本発明のポリ酸は、毛乳頭細胞増殖活性を有し、毛の成長を促進する。従って、種々の脱毛症の治療や予防に有用である。   The polyacid of the present invention has hair papilla cell proliferation activity and promotes hair growth. Therefore, it is useful for treatment and prevention of various alopecia.

ポリ酸は、特定の多面体が稜及び頂点を共有して積み木のように多数縮合してできた多面体の集合であり、その構造及び物性の点で、通常の金属酸化物とよく類似する。大きな相違点は、金属酸化物が無限に広がったバルク構造を持つのに対し、ポリ酸は一個の分子を形成する点にある。ポリ酸の構造はX線構造解析で正確に測定することができるため、ポリ酸は、金属酸化物の特性を分子レベルで議論するには最適なモデルとなる得、「金属酸化物の分子モデル」とも言われる。ポリ酸の多面体は、バナジウムイオン(V5+)、ニオブイオン(Nb5+)、モリブデンイオン(Mo6+)、タングステンイオン(W6+)、タンタルイオン(Ta5+)等の遷移金属イオンに酸化物イオン(O2−)が4〜6配位してできる四面体、四角錐、八面体等である。ポリ酸の構造、物性等については、例えば、「ポリ酸の化学 金属酸化物分子と集合体の構造と機能」日本化学会編 季刊化学総説 No.20, 1993年、学会出版センター;M. T. Pope, 「Heteropoly and Isopolyoxometalates」 1983, Springer-Verlag, Berlin;「Polyoxometalates」 Chem. Rev., 98, 307-325 (1998)等に詳細が記載されている。ポリ酸は、一般的に、上記金属原子と酸素原子のみから構成されるイソポリ酸と、上記金属原子に更にヘテロ原子を含むヘテロポリ酸とに分類される。 A polyacid is a collection of polyhedrons formed by condensation of many polyhedrons like a building block sharing a ridge and apex, and is very similar to ordinary metal oxides in terms of structure and physical properties. The major difference is that the metal oxide has an infinitely spread bulk structure, whereas the polyacid forms one molecule. Since the structure of polyacids can be accurately measured by X-ray structural analysis, polyacids can be an optimal model for discussing the properties of metal oxides at the molecular level. Is also said. The polyhedron of polyacid is composed of transition metal ions such as vanadium ions (V 5+ ), niobium ions (Nb 5+ ), molybdenum ions (Mo 6+ ), tungsten ions (W 6+ ), tantalum ions (Ta 5+ ), oxide ions ( O 2− ) is a tetrahedron, quadrangular pyramid, octahedron, etc. formed by 4-6 coordination. For the structure and physical properties of polyacids, see, for example, “Chemical Metal Oxide Molecules and Structures and Functions of Polyacids”, Chemical Society of Japan, Quarterly Chemical Review No.20, 1993, Society Publishing Center; MT Pope, “Heteropoly and Isopolyoxometalates” 1983, Springer-Verlag, Berlin; “Polyoxometalates” Chem. Rev., 98, 307-325 (1998). Polyacids are generally classified into isopolyacids composed only of the metal atoms and oxygen atoms, and heteropolyacids further containing heteroatoms in the metal atoms.

ポリ酸は、通常、陰イオンとして存在するため、その負電荷を補償するべく、結晶中では、対カチオンとしてプロトン(H)、ナトリウム、カリウム、セシウム等のアルカリ金属イオン;カルシウム、ストロンチウム、バリウム等のアルカリ土類金属イオン、メチルアンモニウム、エチルアンモニウム、ジメチルアンモニウム、イソプロピルアンモニウム等のアルキルアンモニウムイオン(R4−n)(n=1〜3)、ベンジルアンモニウムイオン等のアラルキルアンモニウムイオンなどの有機カチオンが周囲を取り囲み、更に水分子等の溶媒分子やアミノ酸等の有機化合物も配位子としてポリ酸の陰イオン骨格に取り込まれてもよく、また溶媒分子や中性有機化合物が格子中に取り込まれてもよい。 Since polyacid is usually present as an anion, in order to compensate for its negative charge, alkali metal ions such as protons (H + ), sodium, potassium, cesium and the like as counter cations in the crystal; calcium, strontium, barium alkaline earth metal ions, ammonium and the like, ethyl ammonium, dimethyl ammonium, alkyl ammonium ions, such as isopropyl ammonium (R 4-n H n n +) (n = 1~3), aralkyl ammonium ions such as benzyl ammonium ions Organic cations such as water may surround the periphery, and solvent molecules such as water molecules and organic compounds such as amino acids may be incorporated into the anion skeleton of the polyacid as a ligand, and solvent molecules and neutral organic compounds may be latticed. It may be taken in.

本発明で使用されるポリ酸は、モリブデンイオン(Mo6+)及び/又はタングステンイオン(W6+)を含むヘテロポリ酸又はイソポリ酸である。当該イソポリ酸としては、下記式(1):
[MmOy]p−・nHO (1)
[式中、MはMo及びWから選ばれる元素を表し;m、y及びpはそれぞれ1〜200、3〜2000、1〜200の整数を表し;及び、nは0〜1000の整数又は0〜1000の整数+1/2を表す。]
で表されるイソポリ酸イオンを含む化合物が好ましい。また、当該へテロポリ酸としては、下記式(2):
[XxMmOy]q−・nHO (2)
[Mは前記定義の通りであり;Xは周期律表のIA、IIA、IIIA、IVA、VA、VIIA、VIIIA、IB、IIB、IIIB、IVB、VB、VIB又はVIIB族の元素を表し;x、m、y及びqはそれぞれ1〜100、1〜200、3〜2000、1〜200の整数を表し(但し、x≦m);及び、nは0〜1000の整数又は0〜1000の整数+1/2を表す。]
で表されるヘテロポリ酸イオンを有する化合物が好ましい。これらのイソポリ酸及びヘテロポリ酸については、その詳細が、山瀬利博、有機合成化学、第43巻第3号(1985)に記載されている。当然のことながら、前述のごとく、水分子等の溶媒分子やアミノ酸等の有機化合物が配位子として、ポリ酸の陰イオン骨格に取り込まれてもよく、また溶媒分子や中性有機化合物が格子中に取り込まれてもよい。
The polyacid used in the present invention is a heteropolyacid or isopolyacid containing molybdenum ions (Mo 6+ ) and / or tungsten ions (W 6+ ). As said isopolyacid, following formula (1):
[MmOy] p- · nH 2 O (1)
[Wherein, M represents an element selected from Mo and W; m, y and p represent integers of 1 to 200, 3 to 2000 and 1 to 200, respectively; and n represents an integer of 0 to 1000 or 0. Represents an integer of ~ 1000 +1/2. ]
The compound containing the isopolyacid ion represented by these is preferable. Moreover, as the said heteropoly acid, following formula (2):
[XxMmOy] q- · nH 2 O (2)
[M is as defined above; X represents an element of Group IA, IIA, IIIA, IVA, VA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, VIB or VIIB of the periodic table; x , M, y and q each represent an integer of 1 to 100, 1 to 200, 3 to 2000, or 1 to 200 (where x ≦ m); and n is an integer of 0 to 1000 or an integer of 0 to 1000 Represents +1/2. ]
The compound which has the heteropolyacid ion represented by these is preferable. Details of these isopolyacids and heteropolyacids are described in Toshihiro Yamase, Synthetic Organic Chemistry, Vol. 43, No. 3 (1985). Naturally, as described above, solvent molecules such as water molecules and organic compounds such as amino acids may be incorporated into the anion skeleton of the polyacid as ligands, and the solvent molecules and neutral organic compounds may be latticed. It may be taken in.

モリブデンイオン含有のイソポリ酸又はヘテロポリ酸としては、特に限定されないが、具体的には、[NHMe[H16Mo1240(MoO]・10HO(化合物番号:D−5);[NH27[NHMe[Mo14242910(HO)49(MeCO]・150HO(D−6);Na[(Hamp)Mo15]・6HO(プロトン化したアデノシン−5’−モノリン酸)(D−7);Na[(POMo15]・13HO(D−8);Na[Mo26(DL−lysine)]・8HO(D−9)(D体/L体=1/1);[Mo(glycylglycylglycine)]・nHO(D−10);[PrNH[Mo24]・3HO;Na[Mo26(L−lysine)]・8HO;[PrNH[SiMo1240]・nHO;[NMe[H16Mo1652]・12HO;[NH[Mo24]・nHO(PM−20);K[Mo24]・4HO(PM−23)が挙げられる。 The molybdenum ion-containing isopolyacid or heteropolyacid is not particularly limited. Specifically, [NHMe 3 ] 4 [H 16 Mo 12 O 40 (MoO 3 ) 4 ] · 10H 2 O (compound number: D— 5); [NH 4 ] 27 [NHMe 3 ] 4 [Mo 142 O 429 H 10 (H 2 O) 49 (MeCO 2 ) 6 ] · 150H 2 O (D-6); Na 2 [(Hamp) 2 Mo 5 O 15 ] · 6H 2 O (protonated adenosine-5′-monophosphate) (D-7); Na 6 [(PO 4 ) 2 Mo 5 O 15 ] · 13H 2 O (D-8); Na 2 [Mo 8 O 26 (DL-lysine) 2 ] · 8H 2 O (D-9) (D-form / L-form = 1/1); [Mo 2 O 6 (glycylyglycylcine) 2 ] · nH 2 O (D − 10); [Pr i NH 3 ] 6 [Mo 7 O 24] · 3H 2 O; Na 2 [Mo 8 O 26 (L-lysine) 2] · 8H 2 O; [Pr i NH 3] 4 [SiMo 12 O 40] · nH 2 O; [NMe 4] 4 [H 16 Mo 16 O 52] · 12H 2 O; [NH 4] 4 [Mo 7 O 24] · nH 2 O (PM-20); K 6 [ Mo 7 O 24 ] · 4H 2 O (PM-23).

タングステンイオン含有のイソポリ酸又はヘテロポリ酸としては、特に限定されないが、具体的には、Na[EuW1036]・18HO(PM−7);Na[CeW1036](PM−11);Na[NdW1036](PM−12);K11H[(VO)(SbW33]・27HO(D−1);K12[(VO)(BiW33]・29HO(D−2);[PrNHH[PTi1038(O]・HO(D−3);K[(GeTi37]・6HO(D−11);Na10[GeW34]・18HO(D−12);K12[(VO)(AsW33]・6HO(D−13);Na[SbW33]・nHO(D−14);Na[BiW33]・nHO(D−15);K12[(VO)(BiW33]・29HO;K[(GeTi37]・6HO;[PrNHH[PTi1038(O]・HO;K[P1862]・15HO;K[SbW24]・12HO;Na[Eu(W18]・32HO;K[PTi1040]・6HO;K18[KSb2186]・nHO;Na[SbW33]・nHO;Na[BiW33]・nHO;K12[(VO)AsW33]・17HO;[PrNH[PTi1140]・nHO;Li[PTi1040]・xHO;[PrNH[PTi1040]・nHO;Na10[H1242]・20HO;[NH12−x[(BiW33Bi(OH)(HO)10]・nHO;K[BW1240]・9HO;K12[Cu(W34]・nHO;K[SiVW1140]・nHO;K[PVW1140]・nHO;K[HSiNiW1140]・nHO;K[BVW1140]・7HO;[NH[HCo1140]・20HO;Na11(NH)[{Mn(HO)}(SbW33]・45HO等が挙げられる。 The isopoly acid or heteropoly acid of tungsten ion-containing, but not limited, specifically, Na 9 [EuW 10 O 36 ] · 18H 2 O (PM-7); Na 9 [CeW 10 O 36] (PM −11); Na 9 [NdW 10 O 36 ] (PM-12); K 11 H [(VO) 3 (SbW 9 O 33 ) 2 ] · 27H 2 O (D-1); K 12 [(VO) 3 (BiW 9 O 33) 2 ] · 29H 2 O (D-2); [Pr i NH 3] 6 H [PTi 2 W 10 O 38 (O 2) 2] · H 2 O (D-3); K 9 H 5 [(GeTi 3 W 9 O 37) 2 O 3] · 6H 2 O (D-11); Na 10 [GeW 9 O 34] · 18H 2 O (D-12); K 12 [(VO ) 3 (AsW 9 O 33) 2] · 6H 2 O D-13); Na 9 [ SbW 9 O 33] · nH 2 O (D-14); Na 9 [BiW 9 O 33] · nH 2 O (D-15); K 12 [(VO) 3 (BiW 9 O 33) 2] · 29H 2 O; K 9 H 5 [(GeTi 3 W 9 O 37) 2 O 3] · 6H 2 O; [Pr i NH 3] 6 H [PTi 2 W 10 O 38 (O 2) 2] · H 2 O ; K 6 [P 2 W 18 O 62] · 15H 2 O; K 7 [SbW 6 O 24] · 12H 2 O; Na 9 [Eu (W 5 O 18) 2] · 32H 2 O; K 7 [PTi 2 W 10 O 40] · 6H 2 O; K 18 [KSb 9 W 21 O 86] · nH 2 O; Na 9 [SbW 9 O 33] · nH 2 O; Na 9 [ BiW 9 O 33 ] · nH 2 O; K 12 [(VO) 3 AsW 9 O 33] · 17H 2 O; [Pr i NH 3] 5 [PTi 2 W 11 O 40] · nH 2 O; Li 7 [PTi 2 W 10 O 40] · xH 2 O; [Pr i NH 3] 7 [PTi 2 W 10 O 40] · nH 2 O; Na 10 [H 2 W 12 O 42] · 20H 2 O; [NH 4] 12-x H x [(BiW 9 O 33) 3 Bi 6 (OH) 3 (H 2 O) 3 V 4 O 10] · nH 2 O; K 5 [BW 12 O 40] · 9H 2 O; K 12 [Cu 3 (W 9 O 34) 2] · nH 2 O; K 5 [SiVW 11 O 40 ] · nH 2 O; K 5 [PVW 11 O 40 ] · nH 2 O; K 6 [H 2 SiNiW 11 O 40 ] · nH 2 O; K 7 [BVW 11 O 40 ] · 7H 2 O; [NH 4 ] 8 [H 2 Co 2 W 11 O 40] · 20H 2 O; Na 11 (NH 4) [{Mn (H 2 O)} 3 (SbW 9 O 33) 2] · 45H 2 O , and the like.

これらのヘテロポリ酸又はイソポリ酸のうちで、K11H[(VO)(SbW33]・27HO;K12[(VO)(BiW33]・29HO;[PrNH]H[PTi1038(O・HO;Na[(POMo15]・13HO;Na[Mo26(DL−lysine)]・8HO;Na[SbW33]・nHO;Na[NiMo32]・nHO;Na[EuW1036]・18HO;Na[CeW1036];Na[NdW1036];K[P1862]・15HO;Na[(Hamp)Mo15]・6HO;[Mo(glycylglycylglycine)]・nHO;K[(GeTi37]・6HO;Na10[GeW34]・18HO;Na[BiW33]・nHO;又はNa11(NH)[{Mn(HO)}(SbW33]・45HOが好ましく、特にNa[(Hamp)Mo15]・6HO、K11H[(VO)(SbW33]・27HO又はNa[EuW1036]・18HOが好ましい。
また、これらのヘテロポリ酸又はイソポリ酸は、二種以上を組み合わせて使用することもできる。
Of these heteropolyacids or isopolyacids, K 11 H [(VO) 3 (SbW 9 O 33 ) 2 ] · 27H 2 O; K 12 [(VO) 3 (BiW 9 O 33 ) 2 ] · 29H 2 O; [Pr i NH 3] 6 H [PTi 2 W 10 O 38 (O 2) 2 · H 2 O; Na 6 [(PO 4) 2 Mo 5 O 15] · 13H 2 O; Na 2 [Mo 8 O 26 (DL-lysine) 2 ] · 8H 2 O; Na 9 [SbW 9 O 33] · nH 2 O; Na 6 [NiMo 9 O 32] · nH 2 O; Na 9 [EuW 10 O 36] · 18H 2 O; Na 9 [CeW 10 O 36]; Na 9 [NdW 10 O 36]; K 6 [P 2 W 18 O 62] · 15H 2 O; Na 2 [(Hamp) 2 Mo 5 O 15] · 6H 2 O; [Mo 2 O 6 (glycylyglycycine) 2 ] · nH 2 O; K 9 H 5 [(GeTi 3 W 9 O 37 ) 2 O 3 ] · 6H 2 O; Na 10 [GeW 9 O 34 ] · 18H 2 O; Na 9 [BiW 9 O 33 ] · nH 2 O; or Na 11 (NH 4 ) [{Mn (H 2 O)} 3 (SbW 9 O 33 ) 2 ] · 45H 2 O, particularly Na 2 [(Hamp) 2 Mo 5 O 15 ] · 6H 2 O, K 11 H [(VO) 3 (SbW 9 O 33 ) 2 ] · 27H 2 O or Na 9 [EuW 10 O 36 ] · 18H 2 O are preferred.
These heteropolyacids or isopolyacids can be used in combination of two or more.

上記ポリ酸は、一般的に、単核の金属酸素酸イオンであるモリブデン酸イオン(MoO 2−)又はタングステン酸イオン(WO 2−)を水や有機溶媒に溶かし、これに酸を添加し、金属酸素酸イオンと酸とを脱水縮合させることにより多核化させて製造することができる。更に、ヘテロポリ酸を製造するには、上記反応にヘテロ原子を加える。得られるポリ酸イオン種は、金属の種類、濃度、温度、pH、反応時間、ヘテロ原子の種類、量論比などによって変化させることができる。 The polyacid is generally a mononuclear metal oxyacid ion molybdate ion (MoO 4 2− ) or tungstate ion (WO 4 2− ) dissolved in water or an organic solvent, and an acid is added thereto. The metal oxyacid ions and the acid can be polynucleated by dehydration condensation. Furthermore, to produce a heteropolyacid, heteroatoms are added to the reaction. The resulting polyacid ion species can be varied depending on the type, concentration, temperature, pH, reaction time, heteroatom type, stoichiometric ratio, etc. of the metal.

本発明の育毛・養毛料へのポリ酸の配合量は、症状の度合い、剤型等によって適宜選択することができるが、育毛・養毛料が液剤の場合には、1×10−4モル量/L〜0.5×10−1モル量/Lとすることが好ましい。 The blending amount of the polyacid in the hair growth / hair restoration of the present invention can be appropriately selected depending on the degree of symptoms, dosage form, etc., but when the hair growth / hair restoration is a liquid, 1 × 10 −4 mol amount / L to 0.5 × 10 −1 molar amount / L is preferable.

本発明の育毛・養毛料は、育毛効果を増強する点から、血行促進剤、抗菌剤、角質溶解剤、抗脂漏剤、局所刺激剤、抗炎症剤、保湿剤、抗男性ホルモン剤等の他の成分と併用してもよい。これら他の成分は毛伸長に直接的に作用するものではなく、ポリ酸成分とは異なる機作を有するものであるから、併用により育毛作用がより強く発現されることが期待される。例えば、血行促進剤は毛母細胞への栄養補給や毛母細胞からの代謝物の輸送を促進することにより、また抗菌剤は頭皮に対する菌の作用を抑制することにより、それぞれ間接的に毛の成長を促すものである。   The hair growth / hair restoration of the present invention is a blood circulation promoter, antibacterial agent, keratolytic agent, antiseborrheic agent, local stimulant, anti-inflammatory agent, moisturizer, anti-androgen agent, etc. from the point of enhancing the hair growth effect. You may use together with another component. Since these other components do not act directly on hair elongation and have a mechanism different from that of the polyacid component, it is expected that the hair-growth action is more strongly expressed by the combined use. For example, a blood circulation promoter indirectly promotes nutrient supply to the hair matrix cells and promotes the transport of metabolites from the hair matrix cells, and an antibacterial agent indirectly suppresses the action of fungi on the scalp, thereby indirectly It encourages growth.

これらの成分のうち、血行促進剤としては、アセチルコリン、センブリエキス、ニンジンエキス、イチョウエキス、塩化カルプロニウム、塩酸ジフェンヒドラミン、γ−オリザノール、サークレチン、クロマカリム、セファランチン、ニコランジル、ビタミンE、ビタミンEニコチネート等のビタミンE誘導体、ピナシジル、ミノキシジル、フタリド類、キナエキス、ショウブ根エキス、トウヒエキス、当薬エキス、ユズ抽出液等が挙げられる。このうち、アセチルコリン、センブリエキス、ニンジンエキス、イチョウエキス、ビタミンE及びその誘導体、セファランチン、ミノキシジル、塩化カルプロニウム、塩酸ジフェンヒドラミン、γ−オリザノール、サークレチン、クロマカリム、セファランチン、ニコランジル、ピナシジル、ミノキシジル、フタリド類、キナエキス、ショウブ根エキス、トウヒエキス、当薬エキス又はユズ抽出液が好ましく、特にセンブリエキス、ニンジンエキス、イチョウエキス、ビタミンE及びその誘導体、セファランチン、ミノキシジル、塩化カルプロニウム又はフタリド類が好ましい。   Among these ingredients, blood circulation promoters include vitamins such as acetylcholine, assembly extract, carrot extract, ginkgo biloba extract, carpronium chloride, diphenhydramine hydrochloride, γ-oryzanol, cercretin, cromakalim, cephalanthin, nicorandil, vitamin E, vitamin E nicotinate, etc. Examples include E derivatives, pinacidil, minoxidil, phthalides, quina extract, ginger root extract, spruce extract, medicinal extract, and yuzu extract. Of these, acetylcholine, assembly extract, carrot extract, ginkgo biloba extract, vitamin E and its derivatives, cephalanthin, minoxidil, carpronium chloride, diphenhydramine hydrochloride, γ-oryzanol, cerretin, cromakalim, cephalanthin, nicorandil, pinacidil, minoxidil, phthalides, quina extract Sorghum root extract, spruce extract, medicinal extract or yuzu extract are preferred, and in particular, sembly extract, carrot extract, ginkgo biloba extract, vitamin E and its derivatives, cephalanthin, minoxidil, carpronium chloride or phthalides.

抗菌剤としては、イソプロピルメチルフェノール、塩化ベンザルコニウム、オクトピロックス、感光色素101、感光色素201、クロルヘキシジン、サリチル酸、ジンクピリチオン、ソルビン酸カリウム、ビオゾール、ヒノキチオール、フェノール等が挙げられる。また局所刺激剤としては、カンファー、l−メントール、ノニル酸ワニリルアミド、ショウキョウチンキ、オランダガラシエキス、カンタリスチンキ、サンショウエキス、ハッカ油、ワサビ大根エキス等が挙げられる。このうち、オクトピロックス、塩化ベンザルコニウム、ジンクピリチオン、サリチル酸又はイソプロピルメチルフェノールが好ましい。   Examples of the antibacterial agent include isopropylmethylphenol, benzalkonium chloride, octopirox, photosensitive dye 101, photosensitive dye 201, chlorhexidine, salicylic acid, zinc pyrithione, potassium sorbate, biosol, hinokitiol, and phenol. Examples of the local stimulant include camphor, l-menthol, nonylic acid vanillylamide, pepper tincture, Dutch pepper extract, cantalis tincture, salamander extract, peppermint oil, wasabi radish extract and the like. Of these, octopirox, benzalkonium chloride, zinc pyrithione, salicylic acid or isopropylmethylphenol is preferred.

角質溶解剤としては、アスピリン等が挙げられる。抗脂漏剤としては、イオウ、チオキソロン、バンサイド、ポリソルベート類、レシチン、カシュウエキス等が挙げられる。抗炎症剤としては、アズレン、グアイアズレン、抗ヒスタミン剤(ジフェンヒドラミンなど)、酢酸ヒドロコルチゾン、プレドニゾロン、オウゴンエキス、カミツレエキス、カワラヨモギエキス、キキョウエキス、キョウニンエキス、クチナシエキス、熊笹抽出液、ゲンチアナエキス、コンフリーエキス、サンザシエキス、シラカバエキス、セイヨウノコギリソウエキス、ゼニアオイエキス、トウニンエキス、桃葉エキス、ビワ葉エキス等が挙げられる。   Examples of keratolytic agents include aspirin. Examples of antiseborrheic agents include sulfur, thioxolone, vanside, polysorbates, lecithin, and cashew extract. Anti-inflammatory agents include azulene, guaiazulene, antihistamines (diphenhydramine, etc.), hydrocortisone acetate, prednisolone, red gonron extract, chamomile extract, sagebrush extract, red pepper extract, red pepper extract, gardenia extract, bear extract, gentian extract, comfrey extract, Examples include hawthorn extract, birch extract, yarrow extract, mallow extract, sea urchin extract, peach leaf extract, loquat leaf extract and the like.

保湿剤としては、オトギリソウ、可溶性コラーゲン、グリセリン、コンドロイチン硫酸、チューベローズポリサッカライド、冬虫夏草、トリサッカライド、尿素、バイオヒアルロン酸、ヒアルロン酸、ビタミンCリン酸エステルカルシウム塩、ピロリドンカルボン酸ナトリウム、プロピレングリコール、延命草エキス、オオムギ抽出液、オレンジ抽出液、海藻エキス、キューカンバーエキス、ゴボウエキス、シイタケエキス、ジオウエキス、デュークエキス、ビワ抽出液、ブドウ葉エキス、プルーンエキス、ヘチマエキス、マイカイエキス、ミニササニシキ、ユリエキス、リンゴエキス等が挙げられる。   As moisturizers, hypericum, soluble collagen, glycerin, chondroitin sulfate, tuberose polysaccharide, cordyceps, trisaccharide, urea, biohyaluronic acid, hyaluronic acid, vitamin C phosphate ester calcium salt, pyrrolidone carboxylate sodium, propylene glycol, life extension Grass extract, barley extract, orange extract, seaweed extract, cucumber extract, burdock extract, shiitake extract, diou extract, duke extract, loquat extract, grape leaf extract, prune extract, loofah extract, maikai extract, mini sasanishiki, lily extract, An apple extract etc. are mentioned.

抗男性ホルモン剤としては、エチニルエストラジオール、酢酸クロルマジノン等が挙げられる。毛包賦活剤としては、N−アセチル−L−メチオニン、アデノシン三リン酸ジナトリウム、アスパラギン酸カリウム、感光色素301、ペンタデカン酸グリセリド、ネタカナール、パントテン酸エチル、パンテノール、ビオチン、モノニトログアヤコールナトリウム、酵母エキス、真珠蛋白抽出液、タイソウエキス、チクセツニンジン、ニンニク成分、プラセンタエキス、ローヤルゼリーエキス等が挙げられる。   Examples of anti-androgen agents include ethinyl estradiol, chlormadinone acetate, and the like. Examples of hair follicle activators include N-acetyl-L-methionine, disodium adenosine triphosphate, potassium aspartate, photosensitive dye 301, glyceride pentadecanoate, netanar, ethyl pantothenate, panthenol, biotin, mononitroguaiacol sodium , Yeast extract, pearl protein extract, lysium extract, chixetsu carrot, garlic component, placenta extract, royal jelly extract and the like.

上記他の成分は一種又は二種以上を組み合わせて用いることが好ましく、また、水又は水−低級アルコール等の溶媒に溶解して使用することが好ましい。   The other components are preferably used alone or in combination of two or more, and are preferably used by dissolving in a solvent such as water or water-lower alcohol.

上記他の成分は、ポリ酸との相乗効果及び頭皮に対する刺激感の点から、本発明の養毛・育毛料中に0.001〜5重量%配合するのが好ましく、特に0.01〜3重量%配合するのが好ましい。   In view of the synergistic effect with the polyacid and the irritation to the scalp, the above-mentioned other components are preferably incorporated in the hair nourishing and hair restorer of the present invention in an amount of 0.001 to 5% by weight, particularly 0.01 to 3%. It is preferable to mix by weight%.

本発明の養毛・育毛料は外用剤として用いられるもので、その剤型は液剤を主とし、ローションが代表的なものであるがクリームやジェルとすることもできる。液剤には更に炭酸ガスを含有させることもできる。   The hair nourishing / hair-growth preparation of the present invention is used as an external preparation, and its dosage form is mainly a liquid preparation and is representative of a lotion, but can also be a cream or gel. The liquid agent can further contain carbon dioxide gas.

本発明の養毛・育毛料には、上記成分の他に、必要に応じ、本発明の効果を損なわない範囲で、通常の化粧料に使用される油性基剤、ゲル化剤、各種乳化剤、香料、パラヒドロキシ安息香酸エステル等の酸化防止剤、染料等の着色剤を添加配合することができ、具体的には蒸留水、エタノール等の低級アルコール類、セタノール等の高級アルコール類、プロピレングリコール等の多価アルコール類、ワセリン、シリコーン、界面活性剤などが挙げられる。   In addition to the above components, the hair nourishing / hair-growth material of the present invention, if necessary, an oily base, a gelling agent, various emulsifiers, and the like used in ordinary cosmetics, as long as the effects of the present invention are not impaired. Perfumes, antioxidants such as parahydroxybenzoic acid esters, and coloring agents such as dyes can be added and blended. Specifically, distilled water, lower alcohols such as ethanol, higher alcohols such as cetanol, propylene glycol, etc. Polyhydric alcohols, petrolatum, silicone, surfactants and the like.

本発明の養毛・育毛料は、前記必須成分及び任意成分を、常法に従い、混合等の操作を施すことにより製造することができる。   The hair nourishing / hair-growth material of the present invention can be produced by subjecting the essential components and optional components to operations such as mixing in accordance with conventional methods.

次に実施例を挙げて本発明を詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。   EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.

製造例1
ポリ酸PM−7は、T. Yamase他, Bulletin of Chemical Society of Japan No.66 444-449 (1993)に記載の方法により合成した。
Production Example 1
Polyacid PM-7 was synthesized by the method described in T. Yamase et al., Bulletin of Chemical Society of Japan No. 66 444-449 (1993).

製造例2
ポリ酸D−1は、T. Yamase他, Chemistry Letter, 56-57 (2001)に記載の方法により合成した。
Production Example 2
Polyacid D-1 was synthesized by the method described in T. Yamase et al., Chemistry Letter, 56-57 (2001).

製造例3
ポリ酸D−7は、T. Yamase他, Bulletin of Chemical Society of Japan No.69 2863-2868 (1996)に記載の方法により合成した。
Production Example 3
Polyacid D-7 was synthesized by the method described in T. Yamase et al., Bulletin of Chemical Society of Japan No. 69 2863-2868 (1996).

製造例4
ポリ酸D−2は、T. Yamase他, Inorganic Chemistry Communication 4, (2001), 551-554に記載の方法により合成した。
Production Example 4
Polyacid D-2 was synthesized by the method described in T. Yamase et al., Inorganic Chemistry Communication 4, (2001), 551-554.

上記以外の化合物については、N. Fukuda, T. Yamase, and Y, Tajima, Biological and Pharmaceutical Bulletin 22(5), 463-470 (1999)に記載の方法に準じて合成した。   Compounds other than the above were synthesized according to the method described in N. Fukuda, T. Yamase, and Y, Tajima, Biological and Pharmaceutical Bulletin 22 (5), 463-470 (1999).

試験例1 毛乳頭細胞増殖促進効果
10週齢Wister系統ラットを屠殺し、そのラットのひげ部分をハサミで切り取り、実体顕微鏡下で毛包を一つずつ摘出した。各毛包に対し、ツベルクリン用注射針(27G)を用いて毛乳頭組織から毛乳頭を実体顕微鏡下で単離した。得られた毛乳頭を、2mg/ml硫酸カナマイシン(明治製菓株式会社)を含むD−PBS(−)(通常使用する濃度の10倍の濃度に調製)に移し、30〜40分間静置した。次いで、0.2mg/ml硫酸カナマイシンを含む10%FCS含有Amnio Max C−100(インビトロジェン社)を24穴プレートに予め1ml/ウェルずつ加え、そこに採取した毛乳頭を3個ずつ入れた。
Test Example 1 Hair Papilla Cell Growth-Promoting Effect A 10-week-old Wistar strain rat was sacrificed, the beard portion of the rat was cut with scissors, and hair follicles were removed one by one under a stereomicroscope. For each hair follicle, the dermal papilla was isolated from the dermal papilla tissue using a tuberculin needle (27G) under a stereomicroscope. The obtained dermal papilla was transferred to D-PBS (-) containing 2 mg / ml kanamycin sulfate (Meiji Seika Co., Ltd.) (prepared to a concentration 10 times the concentration normally used) and allowed to stand for 30 to 40 minutes. Next, Amno Max C-100 (Invitrogen) containing 10% FCS containing 0.2 mg / ml kanamycin sulfate was added to each 24-well plate in advance at a rate of 1 ml / well, and three collected hair papilla were placed therein.

次いで、各ウェルの底に毛乳頭を早く沈降させるために、プレートごとに遠心(800〜1,000rpm、5分間)し、37℃、5%COの条件下で3〜5週間培養した。尚、培養中にプレート中の周囲のウェルが乾燥しないように、周囲のウェルにはD−PBS(−)を1〜2ml/ウェルずつ入れた。この期間中、培地交換(1回/7日)を除いてプレートを動かさなかった。 Subsequently, in order to quickly settle the hair papilla at the bottom of each well, each plate was centrifuged (800 to 1,000 rpm, 5 minutes) and cultured at 37 ° C. under 5% CO 2 for 3 to 5 weeks. In addition, 1-2 ml / well of D-PBS (−) was added to the surrounding wells so that the surrounding wells in the plate were not dried during the culture. During this period, the plate was not moved except for medium change (1 time / 7 days).

3〜5週間培養後、単層培養となった毛乳頭細胞の培地を吸引除去し、1mlのD−PBS(−)を各ウェルに注入して毛乳頭細胞表面を洗浄した。洗浄後のD−PBS(−)を吸引後、37℃に加温したトリプシンEDTA溶液(0.1%トリプシン及び0.02%EDTA含有)を1ウェルあたり0.3〜0.5ml加え、37℃、5%COの条件下にて5〜15分静置した。その後、各ウェルの底に付着しているコロニー部分を重点的にピペッティングし、付着している毛乳頭細胞を剥離した。 After culturing for 3 to 5 weeks, the medium of the dermal papilla cells that had become a monolayer was removed by suction, and 1 ml of D-PBS (−) was injected into each well to wash the surface of the dermal papilla cells. After aspirating the washed D-PBS (−), trypsin EDTA solution (containing 0.1% trypsin and 0.02% EDTA) heated to 37 ° C. was added in an amount of 0.3 to 0.5 ml per well. ° C., and 5-15 minutes to stand at a 5% CO 2 conditions. Then, the colony part adhering to the bottom of each well was pipetting intensively, and the adhering hair papilla cells were detached.

回収した上記細胞を、10%ウシ胎児血清(FCS)含有Amnio Max C−100(インビトロジェン社)を10ml加えた遠心管(FALCON社、製品番号2097)に入れ、1,000rpmで3分間遠心した。遠心後、上清を吸引によって除去し、約2〜3mlの10%FCS含有Amnio Max C−100を加え、十分に細胞を分散させた。0.2ml中、2x10個の細胞を96穴プレートに入れ、37℃、5%COの条件下で1日培養した。 The collected cells were placed in a centrifuge tube (FALCON, product No. 2097) containing 10 ml of Amno Max C-100 (Invitrogen) containing 10% fetal calf serum (FCS), and centrifuged at 1,000 rpm for 3 minutes. After centrifugation, the supernatant was removed by aspiration, and about 2-3 ml of Amio Max C-100 containing 10% FCS was added to fully disperse the cells. In 0.2 ml, 2 × 10 4 cells were placed in a 96-well plate and cultured for 1 day under conditions of 37 ° C. and 5% CO 2 .

このようにして培養した毛乳頭細胞に対し、対照群(ポリ酸の添加なし)、被検体群を各濃度で添加した(n=3)。ここで、被検体量1μl(エタノール/水=1/4)とは、濃度に換算して5ナノモル量であり、特に断らない限り、2μlは10ナノモル量である。尚、被検体の添加濃度は、マウス神経芽細胞(Neuro 2A)を10%FCS添加MEM培地にて2x10細胞/ウェル(100μl)になるように96ウェルプレートに培養し、翌日PM化合物の段階希釈液(各群、n=6)を100μl添加した後、37℃、5%COの条件下で培養を続け、毎日、顕微鏡下に細胞変性効果を観察、スコアリングし、6ウェル中、3ウェルに細胞変性(50%)が起こる薬物濃度とした。使用量は、細胞変性(50%)が起こる量の、何れも6桁程度少ない量とした。 A control group (no addition of polyacid) and a subject group were added to the dermal papilla cells cultured in this manner at each concentration (n = 3). Here, the amount of analyte 1 μl (ethanol / water = 1/4) is a 5 nanomolar amount in terms of concentration, and 2 μl is a 10 nanomolar amount unless otherwise specified. The concentration of the test sample was determined by culturing mouse neuroblasts (Neuro 2A) in a 96-well plate at 2 × 10 4 cells / well (100 μl) in 10% FCS-added MEM medium, After adding 100 μl of the diluted solution (each group, n = 6), the culture was continued under the conditions of 37 ° C. and 5% CO 2 , and the cytopathic effect was observed and scored under a microscope every day. The drug concentration was such that cell degeneration (50%) occurred in 3 wells. The amount used was an amount that is about six orders of magnitude less than the amount at which cell degeneration occurs (50%).

これらの実験群を37℃、5%COの条件下で2日間培養し、Cell Counting kit−8(同仁化学研究所社)を用いて、培養終了時、培地の吸光度(O.D.450nm/620nm)を測定することにより、生細胞数を計測した。結果を表1に示す。 These experimental groups were cultured at 37 ° C. under 5% CO 2 for 2 days, and using Cell Counting kit-8 (Dojindo Laboratories), the absorbance of the medium (OD 450 nm at the end of the culture). The number of viable cells was measured by measuring (/ 620 nm). The results are shown in Table 1.

Figure 2007191434
Figure 2007191434

表1から明らかなように。いずれのポリ酸も、顕著な毛乳頭細胞増殖促進活性を示した。   As is clear from Table 1. All of the polyacids showed a significant dermal papilla cell proliferation promoting activity.

試験例2 毛幹伸長効果
10週齢Wister系統雄ラットを屠殺し、そのラットのひげ部分をハサミで切り取り、実体顕微鏡下で毛包を一つずつ摘出した。次いで、ポリカーボン膜(Corning社、Transwell(登録商標)、製品番号3422、膜部分:直径6.5mm、孔径8.0μm)を敷いた直径1.5cmの培養皿に1mlの培地(10%FCS含有Amnio Max C−100)を入れ、このポリカーボン膜の上に毛包を置いた。K[(GeTi37]・6HO(D−11)は、濃度が5nMになるように当該培地中に添加した。37℃、5%COの条件下で10日間培養し、ひげの伸長を測定した(n=5)。ひげの伸長度は、対照群(被検体無添加群)を100%とした場合の相対値で表わした。D−11を培地に添加した場合には、明らかなひげ伸長促進効果が認められた(表2)。
Test Example 2 Hair shaft elongation effect 10-week-old Wistar strain male rats were sacrificed, the beard portions of the rats were cut with scissors, and hair follicles were removed one by one under a stereoscopic microscope. Next, 1 ml of culture medium (10% FCS) was placed on a 1.5 cm diameter culture dish on which a polycarbonate film (Corning, Transwell (registered trademark), product number 3422, membrane part: diameter 6.5 mm, pore diameter 8.0 μm) was laid. Containing Amni Max C-100), and a hair follicle was placed on the polycarbonate film. K 9 H 5 [(GeTi 3 W 9 O 37 ) 2 O 3 ] · 6H 2 O (D-11) was added to the medium so as to have a concentration of 5 nM. The cells were cultured at 37 ° C. under 5% CO 2 for 10 days, and the elongation of the whiskers was measured (n = 5). The elongation degree of the whiskers was expressed as a relative value when the control group (no subject added group) was 100%. When D-11 was added to the medium, a clear whisker elongation promoting effect was observed (Table 2).

Figure 2007191434
Figure 2007191434

試験例3 マウス発毛試験
8週齢C3H/HeNCrj系統雄マウスの背部毛を、電気バリカンを用いて2x4cmにわたり剃毛した。次いで、その翌日より、表3の被検体の0.05重量%溶液(50%エタノール)を剃毛部位に1日1回、20mlずつ4週間にわたり塗布した。毛再生を観察するため、上記剃毛部位を一定倍率、一定照度下で撮影し、画像解析装置GS-800 Calibrated Densitometer及び画像解析ソフトQuantity One(BioRad社製)を用いて毛再生活性を数値化した。尚、溶媒(25%エタノール)のみを塗布した群を対照とし、ミノキシジルを塗布した群を比較例とした。結果を表3に示す。
Test Example 3 Mouse Hair Growth Test The back hair of 8-week-old C3H / HeNCrj strain male mice was shaved over 2 × 4 cm 2 using an electric clipper. Then, from the next day, a 0.05 wt% solution (50% ethanol) of the subject shown in Table 3 was applied to the shaved site once a day for 20 weeks at a time for 4 weeks. In order to observe hair regeneration, the above-mentioned shaved part was photographed at a constant magnification and constant illuminance, and the hair regeneration activity was quantified using the image analysis device GS-800 Calibrated Densitometer and image analysis software Quantity One (BioRad). did. In addition, the group which apply | coated only the solvent (25% ethanol) was made into the control, and the group which apply | coated the minoxidil was made into the comparative example. The results are shown in Table 3.

Figure 2007191434
Figure 2007191434

表3から明らかなように、本発明の養毛・育毛料はいずれも、ミノキシジルに比べて毛再生活性が高かった。   As is apparent from Table 3, all of the hair nourishing and hair restorers of the present invention had higher hair regeneration activity than minoxidil.

Claims (4)

タングステンイオン(W6+)及び/又はモリブテンイオン(Mo6+)を含有するイソポリ酸又はヘテロポリ酸を含む、養毛・育毛料。 A hair nourishing and hair restorer comprising an isopolyacid or heteropolyacid containing tungsten ions (W 6+ ) and / or molybdenum ions (Mo 6+ ). 前記イソポリ酸が、下記式(1):
[MmOy]p−・nHO (1)
[式中、MはMo及びWから選ばれる元素を表し;m、y及びpはそれぞれ1〜200、3〜2000、1〜200の整数を表し;及び、nは0〜1000の整数又は0〜1000の整数+1/2を表す。]
で表されるイソポリ酸イオンを含む化合物である、請求項1記載の養毛・育毛料。
The isopolyacid is represented by the following formula (1):
[MmOy] p- · nH 2 O (1)
[Wherein, M represents an element selected from Mo and W; m, y and p represent integers of 1 to 200, 3 to 2000 and 1 to 200, respectively; and n represents an integer of 0 to 1000 or 0. Represents an integer of ~ 1000 +1/2. ]
The hair nourishing and hair restorer according to claim 1, which is a compound containing an isopolyacid ion represented by the formula:
前記へテロポリ酸が、下記式(2):
[XxMmOy]q−・nHO (2)
[Mは前記定義の通りであり;Xは周期律表のIA、IIA、IIIA、IVA、VA、VIIA、VIIIA、IB、IIB、IIIB、IVB、VB、VIB又はVIIB族の元素を表し;x、m、y及びqはそれぞれ1〜100、1〜200、3〜2000、1〜200の整数を表し(但し、x≦m);及び、nは0〜1000の整数又は0〜1000の整数+1/2を表す。]
で表されるヘテロポリ酸イオンを含む化合物である、請求項1記載の養毛・育毛料。
The heteropolyacid is represented by the following formula (2):
[XxMmOy] q- · nH 2 O (2)
[M is as defined above; X represents an element of Group IA, IIA, IIIA, IVA, VA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, VIB or VIIB of the periodic table; x , M, y and q each represent an integer of 1 to 100, 1 to 200, 3 to 2000, or 1 to 200 (where x ≦ m); and n is an integer of 0 to 1000 or an integer of 0 to 1000 Represents +1/2. ]
The hair nourishing and hair restorer according to claim 1, which is a compound containing a heteropolyacid ion represented by the formula:
前記イソポリ酸又は前記へテロポリ酸が、K11H[(VO)(SbW33]・27HO、K12[(VO)(BiW33]・29HO、[PrNH]H[PTi1038(O・HO、Na[(POMo15]・13HO、Na[Mo26(DL−lysine)]・8HO、Na[SbW33]・nHO、Na[NiMo32]・nHO、Na[EuW1036]・18HO、Na[CeW1036]、Na[NdW1036]、K[P1862]・15HO、Na[(Hamp)Mo15]・6HO、[Mo(glycylglycylglycine)]・nHO、K[(GeTi37]・6HO、Na10[GeW34]・18HO、Na[BiW33]・nHO、又はNa11(NH)[{Mn(HO)}(SbW33]・45HOである、請求項1〜3のいずれか1項記載の養毛・育毛料。 The isopolyacid or the heteropolyacid is K 11 H [(VO) 3 (SbW 9 O 33 ) 2 ] · 27H 2 O, K 12 [(VO) 3 (BiW 9 O 33 ) 2 ] · 29H 2 O , [Pr i NH 3] 6 H [PTi 2 W 10 O 38 (O 2) 2 · H 2 O, Na 6 [(PO 4) 2 Mo 5 O 15] · 13H 2 O, Na 2 [Mo 8 O 26 (DL-lysine) 2 ] · 8H 2 O, Na 9 [SbW 9 O 33 ] · nH 2 O, Na 6 [NiMo 9 O 32 ] · nH 2 O, Na 9 [EuW 10 O 36 ] · 18H 2 O, Na 9 [CeW 10 O 36 ], Na 9 [NdW 10 O 36 ], K 6 [P 2 W 18 O 62 ] · 15H 2 O, Na 2 [(Hamp) 2 Mo 5 O 15 ] · 6H 2 O, [Mo 2 O 6 ( lycylglycylglycine) 2] · nH 2 O , K 9 H 5 [(GeTi 3 W 9 O 37) 2 O 3] · 6H 2 O, Na 10 [GeW 9 O 34] · 18H 2 O, Na 9 [BiW 9 O 33] · nH 2 O, or Na 11 (NH 4) [{ Mn (H 2 O)} 3 (SbW 9 O 33) 2] is a · 45H 2 O, any one of claims 1 to 3 Hair restoration and hair growth.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008041608A1 (en) * 2006-09-28 2008-04-10 Yugen Gaisha Matsui Skin external preparation and hair-care product
JP2015213176A (en) * 2009-06-19 2015-11-26 大日本印刷株式会社 Organic electronic device, and method for manufacturing the same
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008041608A1 (en) * 2006-09-28 2008-04-10 Yugen Gaisha Matsui Skin external preparation and hair-care product
JP2015213176A (en) * 2009-06-19 2015-11-26 大日本印刷株式会社 Organic electronic device, and method for manufacturing the same
DE102015000812A1 (en) * 2015-01-21 2016-07-21 Smart Material Printing B.V. Hydrous cleaning and personal care products with biocidal activity
WO2023047708A1 (en) * 2021-09-22 2023-03-30 Vbジャパンテクノロジー株式会社 Anti-aging agent, cosmetic product, wet towel, and hygiene product
JP2023045479A (en) * 2021-09-22 2023-04-03 Vbジャパンテクノロジー株式会社 Anti-aging agent, cosmetic product, anti-aging wet towel, and anti-aging hygiene product
JP7278638B2 (en) 2021-09-22 2023-05-22 Vbジャパンテクノロジー株式会社 Anti-aging wet towels and anti-aging sanitary products
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