TW200812988A

TW200812988A - Antimicrobial/anticeptic agent

Info

Publication number: TW200812988A
Application number: TW96116868A
Authority: TW
Inventors: Makoto Takeuchi; Noriko Mori; Hiromi Tatsukawa
Original assignee: Hayashibara Biochem Lab
Priority date: 2006-05-11
Filing date: 2007-05-11
Publication date: 2008-03-16
Also published as: JPWO2007132710A1; JP5145214B2; WO2007132710A1; TWI427071B

Abstract

The object is to provide a bactericidal/preservative agent whose bactericidal/preservative ingredient is hardly degraded even when exposed to an environmental light such as an artificial light and natural light, and also provide use of the bactericidal/preservative agent. Provided is a bactericidal/preservative agent comprising a specific cyanin dye as a bactericidal/preservative ingredient and rutin or a sugar derivative thereof as an ingredient for improving the light resistance of the cyanin dye. Also provided is an agent for external application to the skin, which comprises the bactericidal/preservative agent.

Description

200812988 九、發明說明【發明所屬之技術領域】本發明係有關新穎的殺菌•防腐劑及其用途。【先前技術】如公知者’化粧品等之皮膚外用劑係力求調製未#微生物者。惟，無論怎麼小心調製，於使用中，仍無法預防微生物的混入•生成爲止，因此，常用防腐劑。又，藉由皮膚外用劑之劑型，於製造途中無法進行物理性減菌，此等一般使用殺菌劑。做爲殺菌劑或防腐劑者適用於皮膚外劑之原料有如·· 苯甲酸、去氫乙酸等之有機酸類、苯基乙醇、苯氧基異丙醇等醇類、羥基苯甲酸酯、氯甲酚等之酚類、氯化苄烷銨、氯化苄乙銨、等之銨鹽類，更有氯己嗪、丙二醇、感光素101號、感光素201號等，其中感光素101號及感光素201 號於低濃度下明顯發揮殺菌•防腐能力，因此始於基礎化粧品、上粧化粧品、髮用化粧品之一般化粧品爲主，可利用對於青春痘之殺菌•抑制生長能力，如：青春痘用劑等之外用藥品中做爲有效成份被廣泛使用之（如：特開平2 - 215706號公報、特開平10-109923號公報、特開2002-212009號公報）。惟，感光素101號、感光素201號等之花青苷色素均藉由化學構造上之理由，相較於上述其他殺菌•防腐劑’其耐光性較小，特別是，溶於溶劑之狀態下，對於自然光、 -5- 200812988 人工光等環境光進行曝露後，短時間內出現分解之問題點【發明內容】有鑑於該狀態’本發明爲解決上述問題之課題係提供一種即使曝露於自然光、人工光等環境光下’其殺菌•防腐成份仍不易分解之殺菌•防腐劑。本發明欲解決之課題更提供一種用於該殺菌·防腐劑之用途，特別是始於化粧品之皮膚外用劑。本發明係藉由提供一種含有做爲殺菌·防腐成份之一般式1或2所示之花青苷色素與提高其花青苷色素之耐光性成份的芸香苷或其糖衍生物所成之殺菌•防腐劑後，而解決該課題。一般式1 : [化3]200812988 IX. INSTRUCTIONS OF THE INVENTION [Technical Field to Be Invented] The present invention relates to novel bactericidal and preservative agents and uses thereof. [Prior Art] A skin external preparation such as a cosmetic product is intended to modulate a non-microorganism. However, no matter how carefully prepared, it is still impossible to prevent the incorporation of microorganisms into the product during use. Therefore, preservatives are commonly used. Further, the dosage form of the external preparation for skin cannot be physically reduced during the manufacturing process, and a bactericide is generally used. As a fungicide or preservative, the raw materials suitable for the skin external agent are organic acids such as benzoic acid and dehydroacetic acid, alcohols such as phenylethanol and phenoxyisopropanol, hydroxybenzoic acid esters and chlorine. Examples of phenols such as cresol, benzalkonium chloride, benzethonium chloride, and the like, and chlorohexazine, propylene glycol, photoreceptor No. 101, and photoreceptor No. 201, among which photoreceptor No. 101 and Sensitizer No. 201 has obvious bactericidal and antiseptic properties at low concentrations. Therefore, it is mainly used in basic cosmetics, makeup cosmetics, and hair cosmetics. It can be used for bactericidal bactericidal and inhibit growth, such as acne. In the case of a drug or the like, it is widely used as an active ingredient (for example, JP-A-2002-215706, JP-A-10-109923, JP-A-2002-212009). However, the anthocyanin pigments such as the photoreceptor No. 101 and the photoreceptor No. 201 are chemically stable, and their light resistance is small compared to the other bactericidal/preservatives described above, in particular, in a solvent state. In the case of natural light, ambient light such as -5-200812988 artificial light, the problem of decomposition occurs in a short time. [Invention] In view of this state, the present invention provides an object of solving the above problems even if exposed to natural light. Under the ambient light such as artificial light, the bactericidal and antiseptic components are still difficult to decompose. The object to be solved by the present invention further provides a use for the bactericidal/preservative, particularly a skin external preparation starting from cosmetics. The present invention provides a bactericidal action by providing a phthalocyanine dye represented by the general formula 1 or 2 as a bactericidal/preservative component and a rutin or a sugar derivative thereof for improving the light resistance component of the anthocyanin pigment. • After the preservative, solve the problem. General formula 1: [Chemical 3]

-6- 200812988 一般式2 : [化4]-6- 200812988 General 2 : [Chem. 4]

(一般式1及2中，1至R5代表互爲相同或相異之脂基，此等脂肪族烴基爲具有取代基亦可，X i •至X 3 -當的陰離子）。本發明更藉由提供一種含有該殺菌•防腐劑所膚外用劑而解決該課題。本發明之殺菌•防腐劑即使曝露於自然光、人環境光下，其殺菌•防腐成份之一般式1及2所示之色素仍不易分解，因此，耐光性之面視之，即使先之使用該花青苷色素有所猶豫，仍無須擔心花青苷分解，具有實際之適用效果。又，使用該殺菌•防腐劑之化粧品等皮膚外用如：溶液、乳液、凍膠、等劑型仍可有效抑制調製中所混入之微生物生長，又’以一般式1或2所示之色素做爲有效成份之醫藥外用品等中具有長時間不殺菌能等之實際效益。肪族烴代表適成之皮工光等花青苷行技術色素之劑即使或使用花青苷易削減 200812988 【實施方式】 [發明實施之最佳形態] 如上述’本發明係有關一種含有做爲殺菌•防腐成份之一般式1或2所示之花青苷色素與提高其花青苷色素之耐光性成份的芸香苷或其糖衍生物所成之殺菌•防腐劑及其用途。一般式1 : [化5](In the general formulae 1 and 2, 1 to R5 represent the same or different aliphatic groups, and the aliphatic hydrocarbon group may have a substituent, and an anion of X i • to X 3 -). The present invention solves this problem by providing an external preparation containing the bactericidal/preservative. The bactericidal/preservative of the present invention is not easily decomposed by the general formulas 1 and 2 of the bactericidal and antiseptic composition even when exposed to natural light or human ambient light. Therefore, the light resistance is regarded as the first use. Anthocyanin pigments are hesitant, and there is no need to worry about the decomposition of anthocyanins, which has practical application effects. Moreover, the external use of the skin such as a solution, an emulsion, a jelly, or the like using the sterilizing and preservative cosmetics can effectively suppress the growth of the microorganisms mixed in the preparation, and the pigment shown in the general formula 1 or 2 is used as the The pharmaceutical ingredients such as the active ingredients have practical benefits such as long-term non-bactericidal energy. An aliphatic hydrocarbon represents an agent for a technical pigment such as a suitable skin dye, such as an anthocyanin-based technical dye. Even if an anthocyanin is used, it is easy to reduce 200812988. [Embodiment] [Best Mode for Carrying Out the Invention] As described above, the present invention relates to a kind of It is a bactericidal/preservative and its use as an anthocyanin pigment represented by the general formula 1 or 2 of the bactericidal/preservative component and a rutin or a sugar derivative thereof for improving the light resistance component of the anthocyanin pigment. General formula 1: [Chemical 5]

一般式2 : [化6]General formula 2: [Chem. 6]

一般式1及2中，1至R5代表互爲相同或相異之脂肪烴基，此等脂肪族烴基爲具有取代基亦可。R i至r5中做爲脂肪族烴者爲具有直鏈狀或支鏈狀之碳數2 〇爲止者，一般碳數爲12爲止者如：甲基、乙基、丙基、異丙基、異丙嫌基 -8 - 200812988 、1 一丙烯基、2-丙烯基、2 -丙炔基、丁基、異丁基、第二—丁基、第三一丁基、2- 丁嫌基、1，3 — 丁一嫌基、戊基、異戊基、新戊基、第三一戊基、1 一甲基戊基、2-甲基戊基、己基、2—戊烯基、2 —戊烯一 4 —基、異己基、5 —甲基己基、庚基、辛基、壬基、癸基、十一基、十二基等例，其中，對於溶劑之溶解性與對於微生物菌體之親和性之面觀之，碳數5至9者爲較佳，特別以碳數7爲最佳者。該脂肪族烴基在不脫離本發明目的之範圍下，藉由其氫原子之1或複數爲羥基或如：甲氧基、三氟甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二-丁氧基、第三-丁氧基、戊氧基、苯氧基、苄氧基等之醚基所取代亦可。另外，如：一般式1及2所示之花青苷色素於分子內具有2個以上相同之環狀基，且其環狀基分別具有脂肪族烴基，由其調製容易度之面觀之，此等脂肪族烴基以互爲相同者宜。一般式1及2中ΧΓ至X，代表適當的陰離子，做爲各個陰離子者如：氟離子、氯離子、溴離子、碘離子、過氯酸離子、過溴酸離子、過碘酸離子、硝酸離子、硫酸離子、燐酸離子、硼酸離子等無機酸離子、乙酸離子、三氟乙酸離子、三氯乙酸離子、苯甲酸離子、羥基苯甲酸離子、碘酸離子、P -甲苯磺酸離子、乙基硫酸離子、天冬胺酸離子、乳清酸離子、煙鹼酸離子等有機酸離子例，其中碘離子爲具有自體殺菌•防腐能力，因此特別理想。 -9 - 200812988 做爲該花青苷色素之具體例者如：化學式1至1 0所示之例。此等對於人體實質上均無不良影響，對於皮膚外用劑中所排除之微生物如：阿爾貝魯氏菌屬、埃希氏菌屬、坎吉達菌屬、棒桿菌屬、單胞菌屬、葡萄球菌屬、桿菌屬之微生物發揮明顯的殺菌能力。化學式1至1 0所示之花青苷色素中又以化學式2及7所示之殺菌•防腐能力特別強，且，對於廣泛用於皮膚外用劑之各溶劑具有適度的溶解性，因此特別理想。又，化學式2及7所示之花青苷色素其分別適於化粧品、醫藥外用品等適於皮膚外用劑之規格者以『pionin』（感光素201號）及『pratonin』（感光素101 號）所成之商品名被販售。 [化學式1]: [化7] [化學式2] [化8]In the general formulae 1 and 2, 1 to R5 represent aliphatic hydrocarbon groups which are the same or different from each other, and these aliphatic hydrocarbon groups may have a substituent. The aliphatic hydrocarbons in R i to r 5 are those having a linear or branched carbon number of 2 ,, and generally have a carbon number of 12 such as methyl, ethyl, propyl or isopropyl. Isopropanyl-8 - 200812988, 1-propenyl, 2-propenyl, 2-propynyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-butyry, 1,3 — butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, hexyl, 2-pentenyl, 2 — a pentene 4-isoyl group, an isohexyl group, a 5-methylhexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group, and the like, wherein the solubility in a solvent and the microbial cell In terms of affinity, a carbon number of 5 to 9 is preferred, and a carbon number of 7 is particularly preferred. The aliphatic hydrocarbon group is a hydroxyl group or a hydroxy group such as a methoxy group, a trifluoromethoxy group, an ethoxy group, a propoxy group, or an isopropoxy group, without departing from the object of the present invention. An ether group such as a butoxy group, an isobutoxy group, a second-butoxy group, a third-butoxy group, a pentyloxy group, a phenoxy group or a benzyloxy group may be substituted. Further, the anthocyanin dyes represented by the general formulas 1 and 2 have two or more identical cyclic groups in the molecule, and the cyclic groups each have an aliphatic hydrocarbon group, and the ease of preparation thereof is observed. These aliphatic hydrocarbon groups are preferably the same as each other. In general formulas 1 and 2, ΧΓ to X represents a suitable anion, such as fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, perbromate ion, periodic acid ion, nitric acid Inorganic acid ions such as ions, sulfate ions, citrate ions, boric acid ions, acetic acid ions, trifluoroacetic acid ions, trichloroacetic acid ions, benzoic acid ions, hydroxybenzoic acid ions, iodic acid ions, P-toluenesulfonic acid ions, ethyl Examples of organic acid ions such as sulfate ion, aspartic acid ion, whey acid ion, and nicotinic acid ion, and iodide ion is particularly desirable because it has autologous sterilization and antiseptic ability. -9 - 200812988 As a specific example of the anthocyanin pigment, examples shown by Chemical Formulas 1 to 10 are used. These have virtually no adverse effects on the human body, and microorganisms excluded from external preparations for the skin such as: Altrogenus, Escherichia, K. genus, Corynebacterium, Monasis, and grapes The microorganisms of the genus Coriolus and the genus Bacillus exert a significant bactericidal ability. Among the anthocyanin pigments represented by Chemical Formulas 1 to 10, the bactericidal and antiseptic properties shown by Chemical Formulas 2 and 7 are particularly strong, and it is particularly desirable for each solvent widely used for external preparations for skin. . Further, the anthocyanin pigments represented by Chemical Formulas 2 and 7 are suitable for "Pionin" (Photoreceptor No. 201) and "pratonin" (Photoreceptor No. 101), respectively, which are suitable for cosmetics and medical external preparations. The product name is sold. [Chemical Formula 1]: [Chemical Formula 2] [Chemical Formula 2] [Chemical 8]

H3C(H2C)2H2C CH2(CH2)2CH3H3C(H2C)2H2C CH2(CH2)2CH3

H3C(H2C)5H2C CH2(CH2)5CH3 -10- 200812988 [化學式3广 [化9]H3C(H2C)5H2C CH2(CH2)5CH3 -10- 200812988 [Chemical Formula 3 Wide [Chemical 9]

H3C(H2C)6H2C CH2(CH2)6CH3 [化學式4]= [化 1〇] h3cH3C(H2C)6H2C CH2(CH2)6CH3 [Chemical Formula 4] = [Chemical Formula 1] h3c

Η3〇(Η2〇)ι〇Η2〇 CH2(CH2)1〇CH3 [化學式5]= [化 11]Η3〇(Η2〇)ι〇Η2〇 CH2(CH2)1〇CH3 [Chemical Formula 5]= [Chem. 11]

-11 - 200812988 [化學式6]: [化 12]-11 - 200812988 [Chemical Formula 6]: [Chem. 12]

^ 7 1 L I U 'J^ 7 1 L I U 'J

[化 13] ,ch3[化13], ch3

S χν ch2(ch2)5ch3 _ CH=CH-C=CH-CH=^S χν ch2(ch2)5ch3 _ CH=CH-C=CH-CH=^

H3C H3C(H2C)5H2CH3C H3C(H2C)5H2C

N CH3 ch2(ch2)5ch3 [化學式8]: [化 14]N CH3 ch2(ch2)5ch3 [Chemical Formula 8]: [Chem. 14]

200812988 [化學式9]= [化 15]200812988 [Chemical Formula 9] = [Chem. 15]

S ,ch3S, ch3

丫 ch2(ch2)7ch3一 S、 f -3 ch2(ch2)7ch3 CH, r /r. 6» —1 LUi字工w [化 16] ,ch3 s丫 ch2(ch2)7ch3_S, f -3 ch2(ch2)7ch3 CH, r /r. 6»——1 LUi character w [化16] ,ch3 s

VV

’ CH2( CH2)1〇CH3- .s、 N+ CH=CH-C=CH-CH=<^' CH2( CH2)1〇CH3- .s, N+ CH=CH-C=CH-CH=<^

Η3σ H3C(H2C)i〇H2CΗ3σ H3C(H2C)i〇H2C

N ! CH3 CH2(CH2)i〇CH3 另外，本發明之芸香苷係指化學式1 1所代表之黃酮-3 -醇配糖體之1種（櫟精一 3 -芸香苷），如可輕易取得之源於寥科、豆科、柑橘科等植物之天然品。 -13- 200812988 [化學式Ilp [化 17]N ! CH3 CH2(CH2)i〇CH3 Further, the rutin of the present invention refers to one of the flavonoid-3-ol glycoside represented by the chemical formula (1), which can be easily obtained. It is derived from the natural products of plants such as Polygonaceae, Leguminosae, and Citrus. -13- 200812988 [Chemical Formula Ilp [Chem. 17]

本發明之芸香苷衍生物係指於化學式11之羥基1或複數鍵結糖殘基所成者’特別由其易於取得之面觀之，以專利申請人之特開平3-2 72 93公報及特開平3 - 1 1 5292 1公報等所載之化學式11之芸香糖殘基中之鍵結於葡萄糖殘基之4 位碳的羥基中之^ -糖基或鍵結於α -糖基所成之α -糖基芸香苷、α -麥芽糖基芸香苷、α -麥芽三糖基芸香苷等爲宜。另外，公知者只知芸香苷爲淡黃色針狀晶之高純品，而，本發明中除知悉該高純品之外，在未脫離本發明目的範圍下，如：寥科、豆科、柑橘科之植物所調製之源於天然之較低純度者’合成品或半合成品’更於澱粉部份分解物之存在下將此等進行酵素處理後取得之如上述之芸香苷糖衍生物與調製方法中特殊之如：未反應之芸香苷、澱粉部份分解物等之摻雜物混成一體所成之組成物亦無妨 -14- 200812988 本發明之殺菌•防腐劑係含有如上 1或複數與芸香苷及/或其糖衍生物所。該殺菌·防腐劑中之芸香苷及/或其其殺菌•防腐劑所使用各個皮膚外用劑，以固形物換算後，通常，對於一般式色素1質量份而言，爲0.01質量份以上：〜1，000質量份，更佳者爲1〜500質量f: 之一般式1或2所示之花青苷色素而言，糖衍生物爲低於〇 · 〇 1質量份則實質上將素之耐光性，反之，超出1，000質量份昇耐光性效果’且其芸香苷或其糖衍生醒目，依其適用對象，此有阻礙商品價般以0.01〜1，000質量份之範圍者宜。本發明之殺菌•防腐劑以液體、固均可發揮明顯的殺菌•防腐能力。特別狀態時，即使曝露於自然光、人工光等減其顯著的的殺菌•防腐能力。做爲溶 1或2所示之花青苷色素及芸香苷或其糖可並未特別限定，各個溶劑被泛用於化劑之可容許之皮膚科學，如：水、乙醇甘油、乙二醇、丙二醇、丁二醇、1，2 -二醇、1，2-庚二醇、u-辛二醇等之，必要時此寺組合後使用之。此等中 .述之花青苷色素之成之殺囷·防腐劑糖衍生物之含量依之種類、用途而異 1或2所示之花青苷菩宜，較佳者以0.1 &。當對於1質量份其芸香苷及/或其無法提高花青苷色則並無法進一步提物之固有黃色更爲値之虞，因此，一體、半固體之形態是用於溶於溶劑之環境光，仍不易削劑者只要其一般式衍生物實質溶解即粧品等之皮膚外用、丙醇、異丙醇、 -戊二醇、1，2—己醇及低分子聚醇例，1，3 —丁二醇等之 -15- 200812988 丁二醇、1，2—戊二醇、ι，2 —己二醇、1，2 —庚二醇、1，2 一辛二醇等之丨，2 一鏈烷二醇其自體具有殺菌•防腐能力 ’特別是後者之1，2 -鏈烷二醇與本發明花青苷色素具有相乘性高度殺菌•防腐效果，因此特別理想。另外，將花青苷色素及芸香苷或其糖衍生物溶於溶劑時，必要時，可適量添加做爲可溶化劑之如：聚環氧乙烷烷醚、聚環氧乙院月桂醚、聚環氧乙院肉豆蔻醚、聚環氧乙烷鱗蠟醚、聚環氧乙烷油烯醚、聚環氧乙烷油烯鯨蠟醚、聚環氧乙烷山窬醚、聚環氧乙烷辛基苯醚、聚環氧乙烷壬基苯醚等之界面活性劑’進行加熱攪拌。本發明之溶液狀殺菌·防腐劑可適當設定花青苷色素之濃度，而做爲殺菌•防腐劑之製品時’針對花青苷色素爲20質量％爲止者宜，通常爲〇.〇1 〜10質量％者宜。針對本發明之殺菌•防腐劑之用途進行說明後，本發明之殺菌•防腐劑對於人體實質上並未有不良影響，可發揮明顯的殺菌•防腐作用，且其殺菌•防腐能力即使曝露於自然光、人工光等之環境光下仍不易減弱，以殺菌•防腐劑爲必要之各類領域，特別是始於化粧品、醫藥外用品之皮膚外用劑之領域爲極有用者。做爲使用本發明殺菌•防腐劑取得之皮膚外用劑者如 :洗面皂、洗臉霜、洗面乳、清潔霜、清潔膠、冷霜、化粧水、按摩霜、乳液、美容液、保濕霜、雪花膏、保養霜、面膜等基礎化粧品及美白化粧品、粉底霜、粉餅、兩用粉底霜、膏狀粉底霜、粉底霜、粉底液、白粉、粉底、口 -16- 200812988 紅、眼影、眼線、睫毛膏、腮紅、指甲油、等上粧化粧品、身體護膚霜、護膚水、按摩霜、爽身粉等身體化粧品、洗髮精、潤髮乳、護髮劑、整髮劑、護髮、髮液、養髮劑、燙髮劑、染髮劑、脫色劑、養髮劑等頭髮用化粧品，肥皂、沐浴乳、洗手肥皂、除臭劑、浴用劑、消臭劑、除毛劑、脫毛劑、刮鬍霜、刮鬍水、刮鬍泡沬等身體保養化粧品、香水、香油、香水皂等芳香化粧品，更如··牙膏、護手乳、青春痘用劑等醫藥外用品爲始之皮膚外用劑例，本發明的殺菌•防腐劑係於該皮膚外用劑中進行微生物之殺菌，有效抑制微生物的生長。該皮膚外用劑係與本發明殺菌·防腐劑，同時於此適度添加泛用之如：水、丙酮、甲苯、丁酮、異丁基甲酮、環己烷、丁醇、乙酸異戊酯、乙酸乙酯、乙酸丁酯等之溶劑、酪梨油、核桃油、橄欖油、可可油、麻油、紅花油、大丑油、余化油、杏仁油、蔑麻子油、紹油、棉子油、木蠘、椰子油、蛋黃油等油脂類、抹香鯨油、北極鯨蠟油、蜜蠟、鯨蠟、含水羊毛脂、荷荷巴油、巴西棕櫚蠟、小燭樹蠟、褐煤鱲、等鱲類、流動石蠟、凡士林、石蠟、天然地蠟、純地蠘、微晶蠟、聚乙烯末、角鯊烯、三十碳烷、十八碳烷、等烴類、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、山窬酸、油酸、1 2 —羥基硬脂酸、妥爾油、含水羊毛脂脂肪酸等之脂肪酸類、乙醇、異丙醇、月桂醇、鯨蠟醇、硬脂醇、異硬脂醇、油烯醇、含水羊毛脂醇、膽固醇、植物留醇、2 —己基癸醇、2 -辛癸醇、氧化乙烯、乙二醇、 -17- 200812988 二乙二醇、三乙二醇、乙二醇單乙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、聚乙二醇、氧化丙烯、丙二醇、聚丙二醇、甘油、丁醇、季戊四醇、山梨糖醇、多糖醇、葡萄糖、蔗糖、麥芽糖、海藻糖等之醇及.糖類、肉豆蔻酸異丙酯、肉豆蔻酸辛基月桂酯、肉豆蔻酸肉豆蔻酯、棕櫚酸異丙酯、硬脂酸丁酯、月桂酸己酯、油酸油酯、油酸癸酯、二甲基辛酸己基癸酯、乳酸鯨蠟酯、乳酸肉豆蔻酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二丁酯、乙酸含水羊毛脂、單硬脂酸乙二醇、單硬脂酸丙二醇、二油酸丙二醇等酯類、阿拉伯膠、安息香膠、達馬膠、愈瘡大脂、愛爾蘭紅藻、刺梧桐膠、西黃蓍膠、卡拉膠、溫桴籽、瓊脂、酪蛋白、糊精、明膠、果膠、果膠酸鈉、澱粉、葡聚糖、支鏈澱粉、褐藻酸鈉、甲基纖維素、乙基纖維素、羧甲基纖維素、羥基乙基纖維素、羥丙基纖維素、硝基纖維素、結晶纖維素、聚乙烯醇、聚乙烯甲醚、聚乙烯吡咯烷酮、聚丙烯酸鈉、羧基乙烯聚合物、聚乙烯亞胺等之聚合物類’脂肪酸系、羧酸系、羧酸鹽系、磺酸系、磺酸鹽系、硫酸酯系、硫酸酯鹽系、燐酸酯系、燐酸酯鹽系、胺鹽系、季銨鹽系、甜菜鹼系、醚系、醚酯系、酯系、嵌段聚合物系、含氮系之陽離子、陰離子、兩性或非離子系界面活性劑、生育酚、芝麻酚、棉子酚、燐脂質、二丁基羥基甲苯、丁基經基茴香醚、沒食子酸丙酯等之抗氧化劑、p -胺基苯甲酸乙酯、水楊酸苯酯、西諾沙酯、愈瘡莫、2 一（2 —經基一 5-甲基苯基）苯並三唑、羥基苯等之紫外 -18- 200812988 線吸收劑、乳酸、酒石酸、琥珀酸、檸檬酸、硼酸、尿囊素、尿囊素經基鋁、氯化鋅、異極礦、硫酸鋅、p -苯酉分磺酸鋅、硫酸鋁鉀、間苯二酚、氯化鐵、螯合劑、檸檬酸鈉、聚磷酸鈉、偏磷酸鈉等金屬離子封鏈劑、軟骨素硫酸鈉、1，3 - 丁二醇、乳酸鈉、多糖醇、木糖醇等保濕劑，更適當配合泛用於化粧品之胺基酸類、維生素類、激素類、香料、色材、防黴劑、抗生素、抗發汗劑、消臭劑、皮膚漂白劑、有機鹼、氣熔膠噴射劑、有機藥品、無機藥品、防蟲劑、創傷治癒劑、抗組織胺劑等後可調製之。做爲該皮膚外用劑之本發明殺菌•防腐劑之量者一般依其皮膚外用劑使用目的而異，通常，化粧品使用時，其花青苷色素濃度以0.002質量％爲止之量，醫藥外用品使用，用以0.005質量％爲止之量。又，本發明之殺菌•防腐劑係指預先混合一般式1或2所示之花青苷色素與芸香苷或其糖衍生物後以獨立形態者，此外，如：將花青苷色素及芸香苷或其糖衍生物各別添加於皮膚外用劑等之適用對象，包括兩者配合所期待之皮膚外用劑形態。又，本發明之殺菌•防腐劑在未跳脫本發明目的範圍下，做爲殺菌· 防腐成份者可使用一般式1及2所示之花青苷色素，同時於此所泛用之其他殺菌•防腐劑如：苯甲酸、脫氫乙酸等有機酸類、苯基乙醇、苯氧基異丙醇等之醇類、羥基苯甲酸酯、氯甲酚等之苯酚類、潔而滅、苄乙銨、等銨鹽類，更組合氯己嗪、丙二醇系之1或複數後使用亦無妨。以下，針對本發明之殺菌•防腐劑之耐光性，以實驗 •19- 200812988 例爲基準進行說明。 <實驗例：耐光性試驗> 對於含有做爲可溶化劑之鯨蠟醇之1，2 -戊二醇/水混液而言，依表1所示配合，分別調製任意之化學式7所示之花青苷色素之感光素101號，或化學式2所示之花青苷色素之感光素201號，與任意含有或未含有芸香苷、α -葡聚糖芸香苷、橙皮苷、或α -葡聚糖橙皮苷之試驗液1至 1〇。再於石英管表面設置光強度之波長413 nm中爲 2.7mW/cm2之螢光燈（定格電力15W、波長380〜700nm) ，分別於石英管取5 0g之試驗液1〜1 〇，將試驗液進行經時採樣，同時藉由螢光燈進行照射人工光40小時。亦即，芸香苷、橙皮苷、及此等糖衍生物之溶液其濃度若超出1質量％則其特徵性黃色將明顯呈現。對於採樣之試驗液，使用市售之逆相高速液體色譜法用柱體（GL科學製，商品名『Inertsil ODS-3V』，利用以甲醇/水混液（體積比85 : 15 )做爲溶出液之高速液體色譜法後，進行定量殘存之花青苷色素。接著，求取照射人工光前取得之色譜法之花青苷色素之波峰面積、與照射人工光20小時或40小時後取得色譜法之花青苷色素之波峰面積，將此等代入數1計算花青苷色素殘存率（％)。其結果不於表2。 -20- 200812988 【1® 配合(質量％) 精製水 96.397 96.397 96.397 96.397 96.497 96.397 96.397 96.397 96.397 96.497 鯨鱲醚 (POE20) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 1，2-戊二醇 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 α -葡萄糖基橙皮苷 1 1 1 0.10 1 1 1 1 0.10 1 橙皮苷 1 瞧 0.10 1 1 1 1 0.10 1 1 α-葡萄糖基芸香苷 1 0.10 1 1 1 細 0.10 I I 1 芸香苷 0.10 1 1 1 1 0.10 1 1 I 1 感光素 201號 1 1 1 1 1 0.003 0.003 0.003 0.003 0.003 感光素 101號 0.003 0.003 0.003 0.003 0.003 1 賺 1 1 1 試驗液 CN cn 寸卜 00 〇\ 〇 -21 - 200812988 花青苷色素殘存率(％) 一「經過一定時間取得色譜法之花青苷色素之波峰面積一. 開始照射前取得色譜法之花青苷色素之波峰面積 [表2] 試驗液花青3 色素殘存率（％) 備考 0小時 2 0小時 4 0小時 1 100 98 97 本發明 2 100 96 95 本發明 3 100 23 5 對照 4 100 2 1 4 對照 5 100 17 0 對照 6 100 97 98 本發明 7 100 98 99 本發明 8 100 25 3 對照 9 100 24 5 對照 10 100 22 0 對照 -22- 200812988 由表2結果顯示’任意配合芸香苷或6^ 一葡聚糖芸香苷之試驗液1、2、6及7即使照射人工光40小時其分析仍於誤差範圍內，幾乎未分解花青苷色素。相較於此’未配合芸香苷或其糖衍生物之對照試驗液5及1 0同樣進行光照射後，經過20小時後，其花青苷色素之量降至最初的4分之1 以下，經過4 0小時後，其花青苷色素急促分解完全無法檢出。加入橙皮苷及^ 一葡聚糖橙皮苷之對照試驗液3、4、 8及9經過4 0小時後雖僅些微檢出花青苷色素’而由提高花青苷色素之耐光性觀點視之’與配合芸香苷及^ -葡聚糖芸香昔之試驗液並無太大差別。如上述，芸香苷與橙皮苷係指關於一般式1及2所示之花青苷色素之感光素201號及感光素101號之耐光性，顯示明顯之差異舉動。如公知者，芸香苷與橙皮苷係指同時具有苯並吡喃骨架，且於其苯並吡喃骨架上鍵結芸香糖殘基所成之類緣體同志。儘管如此，兩者顯示如此不同舉動完全出乎意料。基於此等實驗證實，針對芸香苷及其糖衍生物之α -葡聚糖芸香苷、α 一麥芽糖基芸香苷及α 一麥芽三糖芸香苷使其濃度於0.001〜0.1質量％之範圍下與上述同法進行試驗後，經過40小時後，70%以上之花青苷色素未分解而殘存之。更取代感光素201號及感光素101號，與化學式1 、化學式3〜6及化學式8〜10所示之花青苷色素與芸香苷、α -葡聚糖芸香苷、α —麥芽糖基芸香苷及α -麥芽三糖芸香苷之組合，以0.001〜0.1質量％之範圍下進行相同 -23- 200812988 試驗後’經由共存芸香苷或α -葡聚糖芸香苷後，證明耐光性明顯提昇，不易分解。另外，雖未顯示實驗數據，化學式1至10所示之花青苷色素之殺菌•防腐能力即使其存在芸香苷或其糖衍生物仍未降低。以下，針對本發明之實施形態，以實施例爲基準進行說明。 [實施例1] <殺囷•防腐劑〉適量之1，2 -戊二醇加入可溶化劑之聚環氧乙烷鯨蠟醚（ΡΟΕ 20 )使濃度爲10質量％，更溶於感光素2〇1號（股份公司林原生物化學硏究所製造，商品名『Pionin』）與α -葡聚糖芸香苷（股份公司林原生物化學硏究所販賣 ’商品名『a G芸香苷』）分別爲濃度1及3質量％者，取得本發明之溶液狀殺菌•防腐劑。兼具α -葡聚糖芸香苷之明顯的抗氧化能，曝露於自然光、人工光等環境光仍不易降低殺菌•防腐能力之本例殺菌•防腐劑極適用於化粧品、醫藥外用品等之皮膚外用劑。 [實施例2] <殺菌•防腐劑> 使用1，3 -丁二醇取代ι，2 一戊二醇之外，與實施例1 同法取得本發明溶液狀之殺菌•防腐劑。 -24- 200812988 兼具α -葡聚糖芸香苷之明顯的抗氧化能，即使曝露於自然光、人工光等之環境光仍不易降低殺菌•防腐能力之本例殺菌•防腐劑極適用於化粧品、醫藥外用品等之皮膚外用劑。 [實施例3] <殺菌•防腐劑> 配合源於槐花之高純度芸香苷（股份公司常盤植物化學硏究所製，純度9 5 %以上）做成1質量％濃度取代α — 聚糖芸香苷之外，與實施例1同法，取得本發明溶液狀之殺菌•防腐劑。兼具芸香苷之明顯的抗氧化能，即使曝露於自然光、人工光等環境光仍不易降低殺菌•防腐能力之本例殺菌. 防腐劑極適用於化粧品、醫藥外用品等皮膚外用劑。 [實施例4] <殺菌•防腐劑> 配合感光素1 〇 1號（股份公司林原生物化學硏究所製 ’商品名『Platonin』）使濃度爲〇.〇4質量％取代感光素 201號，同時，α —葡聚糖芸香苷濃度變更爲20質量％之外，與實施例1同法取得本發明溶液狀之殺菌•防腐劑。兼具α -葡聚糖芸香苷之明顯的抗氧化能，即使曝露於自然光、人工光等環境光仍不易降低殺菌•防腐能力之本例殺菌•防腐劑極適用於化粧品、醫藥外用品等之皮膚 -25- 200812988 外用劑。 [實施例5] <化粧水> 對於以下所示化粧水之基本處方，依常法將實施例1 之方法取得之殺菌•防腐劑做成〇 · 〇〇 5質量％之濃度配合後，取得本發明之化粧水。配合成份配合量甘油 2.0質量份丙二醇 6.0質量份二丙二醇 2.0質量份聚環氧乙烷聚丙二醇 1.0質量份聚環氧乙烷山梨聚糖單油酸酯（20EO) 2.0質量份乙醇 15.0質量份香料 0.1質量份精製水 7 1.9質量份具良好的皮膚洗淨力，無刺激皮膚之本例化粧水，即使長時間使用仍不易生長微生物。 [實施例6] <保濕乳霜> 對於以下所示保濕乳霜之基本處方，依常法藉由配合 -26- 200812988 實施例2之方法取得之殺菌·防腐劑0.008質量％濃度後，取得本發明之保濕乳霜。配合成份配合量硬脂酸 2.0質量份硬脂醇 7.0質量份含水羊毛脂 2.0質量份三十碳烷 5.0質量份辛基十二烷醛 6.0質量份聚環氧乙烷鯨蠟醚（25 EO) 3.0質量份新油型單硬脂酸甘油 2.0質量份香料 0.3質量份丙二醇 5.0質量份精製水 67.7質量份具良好的保濕性與延展性，不刺激皮膚之本例保濕乳霜經長時間使用仍不易生長微生物。 [實施例7] <敷面劑> 對於以下所示剝離形態之敷面劑基本處方，依常法藉由配合實施例3之方法取得殺菌•防腐劑之0.004質量％濃度後，取得本發明之敷面劑。 -27- 200812988 配合成份配合量聚乙烯醇 15.0質量份羧甲基纖維素鈉 5.0質量份丙二醇 3.0質量份乙醇 1〇.〇質量份香料 0.5質量份精製水 6 6.5質量份具良好的皮膚洗淨力，附與滋潤皮膚之本例敷面劑於長時間保存仍不易生長微生物。 [實施例8] <粉底霜〉對於以下所示之乳液狀粉底霜基本處方，依常法藉由配合實施例1之方法取得之殺菌•防腐劑之〇 .004質量％濃度後，取得本發明之粉底霜。配合成份配合量硬脂酸 2.4質量份單硬脂酸丙二醇 2.0質量份十六硬脂醇 0.2質量份液狀含水羊毛脂 2.0質量份流動石蠟 3.0質量份肉豆蔻酸異丙酯 8.5質量份對羥基苯甲酸丙酯適量 -28- 200812988 精製水 6 4.1質量份錢基纖維素鈉 0.2質量份膨潤土 0.5質量份丙二醇 4.0質量份三乙胺 1 . 1質量份對羥基苯甲酸甲酯適量氧化鈦 8 . 〇質量份滑石 4.0質量份具有良好的皮膚延展性與附著性，未刺激皮膚之本例粉底霜’經長時間使用仍不易生長微生物。 [實施例9] <洗髮精> 對於以下所示之透明洗髮精基本處方，依常法藉由配合實施例4方法取得之殺菌·防腐劑〇.〇〇7質量％濃度後，取得本發明洗髮精。配合成份配合量烷醚硫酸鈉 16.0質量份月桂酸二乙醇醯胺 4.0質量份丙二醇 2. 〇質量份精製水 78.0質量份 -29- 200812988 具良好洗淨力，不刺激皮膚之本例透明洗髮精經長時間使用仍不易生長微生物。 [實施例1〇] <青春痘用劑> 對於以下所示之青春痘用劑基本處方，依常法藉由配合相同於實施例1所使用之α -葡聚糖芸香苷0.015質量％之濃度後，取得本發明青春痘用劑。配合量 0.1質量份 0.0 0 5質量份 0.5質量份 0.2質量份 5 . 〇質量份 5.0質量份 89.2質量份配合成份甘草酸二鉀化學式2所示之花青苷色素濃度甘油聚環氧乙烷鯨蠟醚（ΡΟΕ20) 1,3-丁二醇乙醇精製水有效預防青舂痘，同時明顯改善，緩和伴隨青春痘之各種症狀之本例青春痘用劑顯示長時間保存仍具穩定之藥理作用。 [產業上可利用性] 本發明之殺菌•防腐劑極適用於化粧品、醫藥外用口% -30- 200812988 等皮膚外用劑，特別是於調製或使用中曝露於自然光、人工光等之皮膚外用劑。皮膚外用劑以外之領域亦適用於務必殺菌•防腐劑之各種物品。The rutin derivative of the present invention refers to a hydroxy group 1 or a complex saccharide residue of the formula 11 which is particularly easy to obtain, and is disclosed in Japanese Patent Laid-Open No. Hei 3-2 72 93 In the sucrose residue of the chemical formula 11 contained in Japanese Patent Publication No. 3 - 1 1 5292 1 or the like, which is bonded to the hydroxyl group at the 4-position carbon of the glucose residue, is bonded to the α-glycosyl group. Preferably, α-glycosyl rutin, α-maltosyl rutin, α-maltotriosyl rutin, and the like. In addition, it is known that only rutin is a high-purity needle-like crystal, and in addition to the high-purity product, the present invention does not deviate from the object of the present invention, such as a plant of the family Polygonaceae, Leguminosae, and Citrus. The sulphur glycoside derivative and the preparation method obtained as described above are obtained by subjecting the natural lower purity 'synthetic or semi-synthetic product' to the enzymatic treatment in the presence of the starch partial decomposition product. For example, the composition of the unreacted rutin, the starch partial decomposition product, and the like may be blended into one. 14-200812988 The bactericidal/preservative of the present invention contains the above 1 or a plurality of rutin and / or its sugar derivatives. In the sterilizing and preservative, the skin external preparations used in the sterilizing and preservatives are generally used in an amount of 0.01 parts by mass or more based on 1 part by mass of the general formula. 1,000 parts by mass, more preferably 1 to 500 mass f: in the case of the anthocyanin pigment represented by the general formula 1 or 2, the sugar derivative is substantially less than 〇·〇1 part by mass. The light resistance, on the other hand, exceeds 1,000 parts by mass of the light-resistance effect', and the rutin or the sugar thereof is conspicuous, and depending on the object to be applied, it is preferably in the range of 0.01 to 1,000 parts by mass. The bactericidal and preservative of the present invention can exert obvious bactericidal and antiseptic ability in liquid and solid. In special conditions, even when exposed to natural light, artificial light, etc., it can reduce its remarkable sterilization and anti-corrosion ability. The anthocyanin pigment and rutin or the saccharide thereof as shown in the solution 1 or 2 are not particularly limited, and each solvent is widely used in the dermatological science of the agent, such as water, ethanol glycerol, and ethylene glycol. , propylene glycol, butanediol, 1,2-diol, 1,2-heptanediol, u-octanediol, etc., if necessary, the temple is used in combination. The aglycone and preservatives of the anthocyanin pigments described herein are different depending on the type and use. The anthocyanins represented by 1 or 2 are preferably 0.1 & When the rutin is 1 part by mass and/or its inability to increase the anthocyanin color, the intrinsic yellow color of the extract can not be further improved. Therefore, the integral, semi-solid form is ambient light for dissolving in a solvent. For those who are still not easy to remove, as long as their general derivatives are dissolved, that is, skin for external use such as makeup, propanol, isopropanol, -pentanediol, 1,2-hexanol and low molecular polyols, 1,3 - Butanediol, etc. -15- 200812988 Butanediol, 1,2-pentanediol, iota, hexanediol, 1,2-heptanediol, 1,2-octanediol, etc., 2 The alkanediol itself has bactericidal and antiseptic ability. In particular, the latter 1,2-alkanediol has a high degree of bactericidal and antiseptic effect with the anthocyanin pigment of the present invention, and therefore is particularly desirable. In addition, when anthocyanin pigment and rutin or a saccharide derivative thereof are dissolved in a solvent, if necessary, an appropriate amount may be added as a solubilizing agent such as polyethylene oxide alkyl ether or polyepoxyether lauryl ether. Poly Ethylene Beans, Myrtle Ether, Poly Ethylene Ethylene Ether, Polyethylene Oxene Ether, Poly Ethylene Oxene Cetyl Ether, Polyethylene Ethylene Oxide, Poly Epoxy The surfactant 'such as ethane octyl phenyl ether or polyethylene oxide decyl phenyl ether is heated and stirred. The solution-like sterilizing and preservative of the present invention can appropriately set the concentration of the anthocyanin pigment, and when it is used as a sterilizing and preservative product, it is preferably 20% by mass for the anthocyanin pigment, and is usually 〇.〇1 〜 10% by mass is suitable. According to the use of the sterilizing and preservative of the present invention, the bactericidal/preservative of the present invention has substantially no adverse effects on the human body, and can exert an obvious bactericidal and antiseptic effect, and its bactericidal and antiseptic ability even if exposed to natural light In the ambient light such as artificial light, it is not easy to be weakened. It is extremely useful in the fields of bactericidal and preservatives, especially in the field of skin external preparations starting from cosmetics and medical supplies. For external use of skin obtained by using the sterilization and preservative of the present invention, such as: facial soap, face cream, facial cleanser, cleansing cream, cleansing gel, cold cream, lotion, massage cream, lotion, beauty lotion, moisturizing cream, cream , maintenance cream, mask and other basic cosmetics and whitening cosmetics, foundation cream, powder cake, dual-use foundation cream, cream foundation cream, foundation cream, liquid foundation, white powder, foundation, mouth-16- 200812988 red, eye shadow, eyeliner, mascara , blush, nail polish, makeup cosmetics, body cream, skin care lotion, massage cream, body powder, body cosmetics, shampoo, conditioner, hair conditioner, hair conditioner, hair care, hair lotion, Hair care products such as hair conditioners, perm agents, hair dyes, bleaching agents, hair conditioners, soaps, shower gels, hand soaps, deodorants, bathing agents, deodorants, depilatory agents, depilatory agents, shaving creams Body care such as shaving water, shaving foam, etc. Cosmetics such as cosmetics, perfumes, sesame oils, perfume soaps, etc., such as toothpaste, hand lotion, acne medication, etc. This hair • bactericidal preservative system to the skin external agent for the sterilization of microorganisms, inhibit the growth of microorganisms. The skin external preparation is combined with the sterilization and preservative of the present invention, and at the same time, it is moderately added as follows: water, acetone, toluene, methyl ethyl ketone, isobutyl ketone, cyclohexane, butanol, isoamyl acetate, acetic acid Ester, butyl acetate and other solvents, avocado oil, walnut oil, olive oil, cocoa butter, sesame oil, safflower oil, big ugly oil, residual oil, almond oil, castor oil, Shao oil, cottonseed oil, wood Oils such as oysters, coconut oil, egg butter, scented whale oil, arctic whale wax, beeswax, whale wax, water-containing lanolin, jojoba oil, carnauba wax, candelilla wax, lignite sputum, etc. Flowing paraffin, petrolatum, paraffin, natural wax, pure germanium, microcrystalline wax, polyethylene, squalene, triacontane, octadecane, hydrocarbons, lauric acid, myristic acid, palmitic acid , fatty acids such as stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, tall oil, aqueous lanolin fatty acid, ethanol, isopropanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, Isostearyl alcohol, oleyl alcohol, aqueous lanolin alcohol, cholesterol, plant alcohol, 2 — Base alcohol, 2-octyl alcohol, ethylene oxide, ethylene glycol, -17- 200812988 diethylene glycol, triethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, polyethylene glycol, propylene oxide, propylene glycol, polypropylene glycol, glycerin, butanol, pentaerythritol, sorbitol, polysaccharide alcohol, glucose, sucrose, maltose, trehalose, etc. , isopropyl myristate, octyl lauryl myristate, myristyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, oleic acid ester, oleic acid ester, two Hexyl decyl methacrylate, cetyl lactic acid, myristyl lactate, diethyl phthalate, dibutyl phthalate, acetic acid containing lanolin, ethylene glycol monostearate, monostearic acid Propylene glycol, dioleic acid propylene glycol and other esters, gum arabic, benzoin, dama gum, acne fat, irish red algae, karaya gum, scutellaria, carrageenan, sorghum seed, agar, casein, Dextrin, gelatin, pectin, sodium pectate, starch, dextran, branched-chain Powder, sodium alginate, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, nitrocellulose, crystalline cellulose, polyvinyl alcohol, polyethylene a polymer such as ether, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer or polyethyleneimine, such as a fatty acid, a carboxylic acid, a carboxylate, a sulfonic acid, a sulfonate or a sulfate. Sulfate salt, phthalate, phthalate, amine salt, quaternary ammonium salt, betaine, ether, ether ester, ester, block polymer, nitrogen-containing cation Anionic, amphoteric or nonionic surfactant, tocopherol, sesame phenol, gossypol, guanidine lipid, dibutylhydroxytoluene, butyl phenyl anisate, propyl gallate, etc., p -Amino benzoic acid ethyl ester, phenyl salicylate, sinofloxacin, guaiac, 2-(2-cyano-5-methylphenyl)benzotriazole, hydroxybenzene, etc. UV-18 - 200812988 Line absorbent, lactic acid, tartaric acid, succinic acid, citric acid, boric acid, allantoin, allantoin Aluminum, zinc chloride, heteropolar ore, zinc sulfate, zinc p-benzoquinone sulfonate, potassium aluminum sulfate, resorcinol, ferric chloride, chelating agent, sodium citrate, sodium polyphosphate, sodium metaphosphate, etc. Metal ion chain-blocking agent, sodium chondroitin sulfate, 1,3-butanediol, sodium lactate, polysaccharide alcohol, xylitol and other moisturizing agents, more suitable for use in cosmetics, amino acids, vitamins, hormones, spices , color materials, anti-mold agents, antibiotics, anti-perspirants, deodorants, skin bleaches, organic bases, gas-melt adhesives, organic drugs, inorganic drugs, insecticides, wound healing agents, antihistamines, etc. It can be modulated later. The amount of the sterilizing and preservative of the present invention as the external preparation for skin is generally different depending on the purpose of the external use of the skin. Usually, when the cosmetic is used, the concentration of the anthocyanin pigment is 0.002% by mass, and the medical external product is used. It is used in an amount of 0.005 mass%. Further, the bactericidal/preservative agent of the present invention refers to an individual form in which an anthocyanin pigment and a rutin glycoside or a saccharide derivative thereof represented by the general formula 1 or 2 are preliminarily mixed, and further, for example, anthocyanin pigment and musk are used. Each of the glycosides or the sugar derivatives thereof is added to an application for external use of the skin, and the like, and the form of the external preparation for skin to be used together. Further, the bactericidal/preservative of the present invention can be used as a bactericidal/antiseptic component in the range of the object of the present invention, and the anthocyanin pigments shown in the general formulas 1 and 2 can be used, and other sterilizations which are generally used herein are also used. • Preservatives such as benzoic acid, dehydroacetic acid and other organic acids, phenylethanol, phenoxyisopropanol and other alcohols, hydroxybenzoic acid esters, chlorocresols and other phenols, clean and sterilized, benzyl b It is also possible to use ammonium or an ammonium salt in combination with one or more of chlorohexazine or propylene glycol. Hereinafter, the light resistance of the sterilizing and preservative of the present invention will be described based on the experimental example 19-200812988. <Experimental Example: Light Resistance Test> The 1,2-pentanediol/water mixture containing cetyl alcohol as a solubilizing agent was blended as shown in Table 1, and each of Chemical Formula 7 was prepared. Anthocyanin pigment No. 101, or anthocyanin pigment No. 201 shown in Chemical Formula 2, with or without rutin, α-glucan rutin, hesperidin, or α - Test solution of dextran hesperidin 1 to 1 Torr. Further, a fluorescent lamp having a light intensity of 2.7 mW/cm 2 at a wavelength of 413 nm (a fixed grid power of 15 W and a wavelength of 380 to 700 nm) was placed on the surface of the quartz tube, and 50 g of the test liquid 1 to 1 〇 was taken in a quartz tube, respectively. The liquid was sampled over time while artificial light was irradiated by a fluorescent lamp for 40 hours. That is, if the concentration of the solution of rutin, hesperidin, and such sugar derivatives exceeds 1% by mass, the characteristic yellow color will be apparent. For the sampled test solution, a commercially available column for reverse phase high-speed liquid chromatography (manufactured by GL Scientific, trade name "Inertsil ODS-3V", using methanol/water mixture (volume ratio 85: 15) as the eluate After the high-speed liquid chromatography, the anthocyanin pigment remaining in the quantification is quantified. Then, the peak area of the anthocyanin pigment obtained by the chromatography obtained before the artificial light is irradiated, and the chromatographic method is obtained after irradiating the artificial light for 20 hours or 40 hours. The peak area of the anthocyanin pigment was calculated by substituting this number into the number 1 to calculate the residual rate of the anthocyanin pigment (%). The results are not shown in Table 2. -20- 200812988 [1® compounding (mass%) refined water 96.397 96.397 96.397 96.397 96.497 96.397 96.397 96.397 96.397 96.497 Whale Ether (POE20) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 1,2-Pentanediol 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 α-Glucosylhesperidin 1 1 1 0.10 1 1 1 1 0.10 1 Hesperidin 1 瞧 0.10 1 1 1 1 0.10 1 1 α-Glucosyl Rutin 1 0.10 1 1 1 Fine 0.10 II 1 Rutin 0.10 1 1 1 1 0.10 1 1 I 1 Photosensitive 201 No. 1 1 1 1 1 0.003 0.003 0.003 0.003 0.003 sensitizer 101 No. 0.003 0.003 0.003 0.003 0.003 1 Earn 1 1 1 Test solution CN cn 寸 00 〇〇 --21 - 200812988 Anthocyanin pigment residual rate (%) - "After a certain period of time to obtain chromatography Peak area of anthocyanin pigment 1. Peak area of anthocyanin pigment obtained by chromatography before starting irradiation [Table 2] Test solution cyanine 3 Residual rate of pigment (%) Preparation 0 hour 2 0 hour 4 0 hour 1 100 98 97 invention 2 100 96 95 invention 3 100 23 5 control 4 100 2 1 4 control 5 100 17 0 control 6 100 97 98 invention 7 100 98 99 invention 8 100 25 3 control 9 100 24 5 control 10 100 22 0 Control-22- 200812988 The results in Table 2 show that the test solutions 1, 2, 6 and 7 of any combination of rutin or 6^-glucan rutin are within the error range even when irradiated with artificial light for 40 hours. Undecomposed anthocyanin pigment. Compared with the control test solutions 5 and 10 which were not combined with rutin or a sugar derivative thereof, the amount of anthocyanin pigment was reduced to 1 or less of the first one after 20 hours. After 40 hours, the anthocyanin pigment was rapidly decomposed and could not be detected. Adding hesperidin and dextran hesperidin control test solutions 3, 4, 8 and 9 after 40 hours, although only slightly detected anthocyanin pigments, and improving the lightfastness of anthocyanin pigments It is considered that it is not much different from the test solution of rutin and gamma glucomannan. As described above, rutin and hesperidin refer to the photosensitivity of the anthocyanin pigment No. 201 and the photoreceptor No. 101 shown in the general formulas 1 and 2, and show a significant difference. As is well known, rutin and hesperidin refer to comrades having a benzopyran skeleton and having a rutose residue bonded to a benzopyran skeleton. Despite this, the two show that such a different move is completely unexpected. Based on these experiments, it was confirmed that the concentration of α-glucan rutin, α-maltosyl rutin and α-maltotriose rutin against rutin and its sugar derivative were in the range of 0.001 to 0.1% by mass. After the test was carried out in the same manner as above, after 40 hours, more than 70% of the anthocyanin pigment remained without being decomposed. Further replacing photoreceptor No. 201 and photoreceptor No. 101, and anthocyanin pigment and rutin, α-glucan rutin, α-maltosyl rutin, which are represented by Chemical Formula 1, Chemical Formulas 3 to 6, and Chemical Formulas 8 to 10. And the combination of α-maltotriose rutin, the same -23-200812988 test after the same -23-200812988 test, after the coexistence of rutin or α-glucan rutin, the light resistance was significantly improved, Not easy to break down. Further, although the experimental data is not shown, the bactericidal and antiseptic ability of the anthocyanin pigments shown in Chemical Formulas 1 to 10 is not lowered even if rutin or a sugar derivative thereof is present. Hereinafter, embodiments of the present invention will be described on the basis of examples. [Example 1] <Acaricide/preservative> An appropriate amount of 1,2-pentanediol was added to a solubilizing agent of polyethylene oxide cetyl ether (ΡΟΕ 20 ) to a concentration of 10% by mass, which was more soluble in photosensitivity.素2〇1 (manufactured by the company Linyuan Biochemical Research Institute, trade name "Pionin") and α-glucan rutin (sold by the company Linyuan Biochemical Research Institute, the trade name "a G rutin") The solution-like bactericidal and preservative of the present invention was obtained at a concentration of 1% and 3% by mass, respectively. It has obvious anti-oxidation energy of α-glucan rutin, and it is not easy to reduce the sterilization and anti-corrosion ability when exposed to ambient light such as natural light or artificial light. This kind of sterilization and preservative is very suitable for skin of cosmetics, medical supplies and the like. External preparation. [Example 2] <Bactericidal and Preservative> The bactericidal/preservative of the solution of the present invention was obtained in the same manner as in Example 1 except that 1,3 -butanediol was used instead of i.sub.2, pentanediol. -24- 200812988 It has obvious anti-oxidation energy of α-glucan rutin, even if it is exposed to ambient light such as natural light or artificial light, it is not easy to reduce the sterilization and anti-corrosion ability. This kind of sterilization and preservative is very suitable for cosmetics, A skin external preparation such as a medical external product. [Example 3] <Bactericidal and Preservative> Compatible with high-purity rutin (made by the company's Phytochemical Research Institute of the company, purity of 95% or more) to make a 1% by mass concentration of α-poly In the same manner as in Example 1, except for the glucoside, the bactericidal/preservative of the solution of the present invention was obtained. It has obvious anti-oxidation energy of rutin, and it is not easy to reduce the sterilization and anti-corrosion ability of this case even if it is exposed to ambient light such as natural light or artificial light. The preservative is extremely suitable for skin external preparations such as cosmetics and medical external products. [Example 4] <Bactericidal and Preservative> In combination with the photoreceptor No. 1 (trade name "Platonin" manufactured by the company Linyuan Biochemical Research Institute), the concentration was 〇.〇4 mass% instead of the photoreceptor 201 In the same manner as in Example 1, the bactericidal/preservative of the solution of the present invention was obtained in the same manner as in Example 1 except that the α-glucan rutin concentration was changed to 20% by mass. It has obvious anti-oxidation energy of α-glucan rutin, and it is not easy to reduce the sterilization and anti-corrosion ability even when exposed to ambient light such as natural light or artificial light. This kind of sterilization and preservative is extremely suitable for cosmetics, medical supplies, etc. Skin-25- 200812988 External preparation. [Example 5] <Cosmetic Water> The basic prescription of the lotion shown below is obtained by mixing the sterilizing and preservative obtained by the method of Example 1 into a concentration of 5% by mass of 〇·〇〇 in accordance with the usual method. The lotion of the present invention is obtained. Formulation amount of glycerin 2.0 parts by mass of propylene glycol 6.0 parts by mass of dipropylene glycol 2.0 parts by mass of polyethylene oxide polypropylene glycol 1.0 part by mass of polyethylene oxide sorbitan monooleate (20EO) 2.0 parts by mass of ethanol 15.0 parts by mass of perfume 0.1 parts by mass of purified water 7 1.9 parts by mass of the lotion having good skin cleansing power and no irritating skin, it is difficult to grow microorganisms even after long-term use. [Example 6] <Moisturizing Cream> With respect to the basic prescription of the moisturizing cream shown below, the concentration of the sterilizing and preservative obtained in the method of Example 2 of -26-200812988 was 0.008% by mass, The moisturizing cream of the present invention is obtained. Ingredient amount of stearic acid 2.0 parts by mass of stearyl alcohol 7.0 parts by mass of aqueous lanolin 2.0 parts by weight of triacontane 5.0 parts by mass of octyldodecanal 6.0 parts by mass of polyethylene oxide cetyl ether (25 EO) 3.0 parts by mass of fresh oil type monostearic acid glycerin 2.0 parts by mass of perfume 0.3 parts by mass of propylene glycol 5.0 parts by mass of purified water 67.7 parts by mass with good moisturizing property and ductility, without irritating the skin, the moisturizing cream of this example is still used for a long time It is not easy to grow microorganisms. [Example 7] <Coating agent> The basic formulation of the face-coating agent in the peeling form shown below was obtained by mixing the concentration of 0.004% by mass of the sterilizing and preservative according to the method of Example 3 by the usual method. The application of the invention. -27- 200812988 Mixing amount of polyvinyl alcohol 15.0 parts by weight sodium carboxymethyl cellulose 5.0 parts by mass of propylene glycol 3.0 parts by mass of ethanol 1 〇 mass part of perfume 0.5 parts by mass of purified water 6 6.5 parts by mass with good skin cleansing The force, attached to the moisturizing skin, is not easy to grow microorganisms after long-term storage. [Example 8] <Powder Cream> The basic formulation of the emulsion-like foundation cream shown below was obtained by the method of the method of Example 1, which was obtained by the method of the method of Example 1, and the concentration of the sterilizing and preservative was 004% by mass. The foundation cream of the invention. Ingredient amount of stearic acid 2.4 parts by mass of monostearic acid propylene glycol 2.0 parts by weight of hexadecyl alcohol 0.2 parts by mass of liquid aqueous lanolin 2.0 parts by weight of liquid paraffin 3.0 parts by mass of isopropyl myristate 8.5 parts by weight of p-hydroxyl Propyl benzoate amount -28- 200812988 Refined water 6 4.1 parts by mass of sodium cellulose 0.2 parts by mass of bentonite 0.5 parts by mass of propylene glycol 4.0 parts by mass of triethylamine 1. 1 part by mass of methyl p-hydroxybenzoate. 〇 mass of talc 4.0 parts by mass has good skin ductility and adhesion, and this foundation cream which does not irritate the skin is not easy to grow microorganisms after long-term use. [Example 9] <Shampoo> The basic formulation of the transparent shampoo shown below, after the concentration of the sterilizing/preserving agent 〇〇.〇〇7 mass% obtained by the method of Example 4 by the usual method, The shampoo of the present invention is obtained. Ingredients: 16.0 parts by mass of lauric acid diethanolamine, 4.0 parts by mass of propylene glycol 2. 〇 parts by mass of refined water 78.0 parts by mass -29- 200812988 Transparent shampoo with good detergency and no irritation to the skin It is still difficult to grow microorganisms after long time use. [Example 1] <Acne Use Agent> For the basic prescription of the acne agent shown below, 0.011% by mass of the α-glucan rutin used in the same manner as in Example 1 was used in accordance with the usual method. After the concentration, the acne agent of the present invention is obtained. The amount of the compound is 0.1 parts by mass, 0.05 parts by mass, 0.5 parts by mass, 0.2 parts by mass, 5 parts by mass, 5.0 parts by mass, 89.2 parts by mass, of the component, the anthocyanin pigment concentration of the dipotassium glycyrrhizinate, and the glycerol-polyethylene oxide whale. Wax Ether (ΡΟΕ20) 1,3-butanediol ethanol refined water is effective in preventing acne, and at the same time significantly improving, and alleviating the symptoms associated with acne. This example of acne has a stable pharmacological effect for long-term preservation. [Industrial Applicability] The bactericidal and antiseptic agent of the present invention is extremely suitable for use in cosmetic and medical external use% -30- 200812988 and other external preparations for skin, especially skin external preparations which are exposed to natural light, artificial light, etc. during preparation or use. . Fields other than skin external preparations are also suitable for various items that must be sterilized and preservatives.

Claims

200812988 X. Patent application scope 1 · A bactericidal and antiseptic agent characterized by containing an anthocyanin pigment as a general formula 1 or 2 as a bactericidal and antiseptic component and a musk enhancing the light resistance component of the cyanine dye Made from glycosides or their sugar derivatives, general formula 1: [Chemical 1]

General formula 2: [Chemical 2]

(In the general formulae 1 and 2, R! to Rs represent an aliphatic hydrocarbon group which are the same or different from each other, and these aliphatic hydrocarbon groups may have a substituent, and χ -1壬 X 3 represents an appropriate anion). 2. For the bactericidal/preservative according to item 1 of the patent application, it is a musk scent containing the general formula 1 or 2 as a killing and antiseptic component and a musk enhancing the anthocyanin pigment light resistance component. Glycosides or their sugar derivatives are exemplified and are dissolved in a suitable solvent. -32-200812988 3. The bactericidal/preservative according to any one of the above-mentioned items of the first or the second aspect of the invention, which contains 0.01 parts by mass or more of rutin or 1 part by mass of the anthocyanin pigment or It is made from sugar derivatives. 4. A bactericidal preservative according to any one of claims 2 or 3, wherein the solvent is any of an alcohol or a low molecular polyol. A skin external preparation comprising a bactericidal/preservative according to any one of claims 1 to 4. -33- 200812988 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display invention. Chemical formula of the formula: formula (1), (2)