TW200803906A - One-part type hair dye utilizing optical energy - Google Patents
One-part type hair dye utilizing optical energy Download PDFInfo
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- TW200803906A TW200803906A TW096109095A TW96109095A TW200803906A TW 200803906 A TW200803906 A TW 200803906A TW 096109095 A TW096109095 A TW 096109095A TW 96109095 A TW96109095 A TW 96109095A TW 200803906 A TW200803906 A TW 200803906A
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- silver
- amino acid
- hair
- color
- hair dye
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G18/00—Cultivation of mushrooms
- A01G18/60—Cultivation rooms; Equipment therefor
- A01G18/64—Cultivation containers; Lids therefor
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G18/00—Cultivation of mushrooms
- A01G18/60—Cultivation rooms; Equipment therefor
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- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Mycology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Cosmetics (AREA)
Abstract
Description
200803906 九、發明說明: 【發明所屬之技術領域】 本發明係一種染髮料,尤其是一種能穩定地利用光能 且不會損傷皮膚與毛髮的單劑型染髮料。 【先前技術】 一般用於對毛髮進行染色的製品可分為作為準藥品 (quas卜drugs)的染髮劑以及作為化妝品的染髮料。200803906 IX. Description of the Invention: The present invention relates to a hair dye, and more particularly to a single-dose hair dye which can stably utilize light energy without damaging the skin and hair. [Prior Art] Products generally used for dyeing hair can be classified into hair dyes as quasi drugs (quads) and hair dyes as cosmetics.
"亥染髮劑可分為氧化染髮劑和非氧化染髮劑。其中該 氧化木艾劑的原理係讓染髮劑中的氧化染料滲入毛髮中, 亚使得經氧化聚合生成的不溶性色素固定於毛髮;而該非 氧化染髮劑的原理係讓非氧化染髮劑中之氧化染料所滲入 毛及中的多酚與鐵離子生產黑色色素。而這些染髮劑由於 顏色、准持日守間較長(約2個月至3個月”故被稱為永久染 髮劑。 二十於每些永久染髮劑而言,因為必須經由將氧 化染料摩入毛髮φ沾 會使得毛髮及其後的化學反應’因此 程度的危害。 膚魚炎等,故對於人體健康有-定 而該染髮料則可分為酸性 中該酸性染髮料是嗜主t a 汉乇交者色枓。其 以進行染髮,:因二的蛋白質與酸性染料的離子鍵結 被稱為半永久:髮;色維持時間較短(約2周至3周),故 著於毛髮表面::;進二:毛:著色料是讓染料中的顏料附 般的洗髮精即可、先:…此為暫時的著色’僅需採用― 先去’因此又被稱為暫時染髮料。 5 200803906"Hai hair dye can be divided into oxidative hair dye and non-oxidative hair dye. The principle of the oxidized woody agent is to allow the oxidative dye in the hair dye to penetrate into the hair, so that the insoluble pigment formed by oxidative polymerization is fixed to the hair; and the principle of the non-oxidative hair dye is to make the oxidative dye in the non-oxidative hair dye The polyphenols infiltrated into the hair and the iron ions produce black pigment. These hair dyes are called permanent hair dyes because of their long color and long-term retention (about 2 months to 3 months). For every permanent hair dye, it is necessary to pass the oxidation dye. Into the hair φ dip will make the hair and the chemical reaction behind it 'so the degree of harm. Skin fish inflammation, etc., so there is a certainty for human health and the hair dye can be divided into acidity. The acid dyeing material is the lord tahan It is used for dyeing hair. The ionic bond between protein and acid dye is called semi-permanent: hair; the color retention time is short (about 2 weeks to 3 weeks), so it is on the hair surface: Into the second: hair: coloring material is to let the dye in the dye attached to the shampoo, first: ... This is a temporary coloring 'only need to use - first go' is therefore also known as temporary hair dye. 5 200803906
以上可參考〔非專利文獻1]FRAGRANCE JOURNAL 2001-8特集中的「染髮劑-染髮料的功能和最近的開發動 向」之第11~15頁。 此外,染髮料中不僅有酸性染料,以往還有使用含銀 鹽類製成的染髮料。該含銀鹽類的染髮料是利用硫化鈉水 溶液之第1液和含有硝酸銀水溶液之第2液所製成的,或 是使用含有硫化鉀醇溶液的f !液和含有硝酸銀水溶液的 第2液所製成的。使用時,先用刷子蘸上第,液潤濕毛髮, 而後再用另外-刷子將帛2液塗佈於毛髮,利用黑色的硫 化銀附著於毛髮表面的角蛋白上,即可將毛髮染專。 然而,利用含銀鹽類所製成的染髮劑進行染色時,毛 髮上會附著有如腐敗之雞蛋的惡臭(硫化氫),該惡臭雖秋 可藉由水洗而除去,但顯然、不是使用者會優先選擇的染髮 料0For the above, refer to pages 11 to 15 of "Functions and Recent Development Trends of Hair Dye-Dyeing Materials" in the FRAGRANCE JOURNAL 2001-8 Special Collection [Non-Patent Document 1]. In addition, dyeing materials contain not only acid dyes, but also hair dyes made of silver-containing salts. The silver salt-containing hair dye is prepared by using the first liquid of the sodium sulfide aqueous solution and the second liquid containing the silver nitrate aqueous solution, or using the f! liquid containing the potassium sulfide alcohol solution and the second liquid containing the silver nitrate aqueous solution. Made of. When using, first use a brush to rub the first, the liquid moisturizes the hair, and then apply the 帛2 solution to the hair with another brush, and attach the black silver sulfide to the keratin on the surface of the hair to dye the hair. . However, when dyeing with a hair dye made of a silver salt, the stench (hydrogen sulfide) such as a spoiled egg adheres to the hair, and the malodor can be removed by washing in autumn, but it is obvious that the user does not Preferred hair dye 0
以上可參考〔非專利文獻2]平野—貫編註「增訂六版 香料製造法」半田屋醫籍店,大正…月出版。 房 以上又可參考〔非專利文獻3W牛山著,萬里閣書 昭合3年5月出版「近代美容法」第292〜297頁。 對於上述之含銀鹽類染髮料的改善方法發展出各種提 案。 例如’有提案提出一種染髮料’其係含有A劑與b劑, 所述之A劑係由含有二胺銀配位鹽和/或乙醇胺銀配位鹽的 水溶液所組成,所述之B劑係含有對苯二胺等染料中間體 的水溶液所組成。 6 200803906 Μ上 二文獻υ特開平G4_312514號公報β 成分作為進3 出含有南化銀、顯色劑等各種添加 方式存在有雙劑型與單劑型,==以料。作為製劑的 利=輕㈣料㈣劑,㈣《等胺基酸。For the above, please refer to [Non-Patent Document 2] Hirano-Kyo, "Additional Six Editions of Spices Manufacturing Method", Half-Tokyo Medical Store, Taisho... published. For more information, please refer to [Non-Patent Document 3W Niu Shan, Wan Li Ge Shu Zhao He published the "Modern Beauty Law" on May 292~297. Various proposals have been made for the above-described improvement method of silver salt-containing hair dyes. For example, 'there is a proposal for a hair dye' which contains an A agent and a b agent, and the A agent is composed of an aqueous solution containing a diamine silver complex salt and/or an ethanolamine silver complex salt, the B agent. It is composed of an aqueous solution containing a dye intermediate such as p-phenylenediamine. 6 200803906 Μ上。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 As a preparation, the product is a light (four) material (four) agent, and (iv) an "amino acid.
又,=考〔專利文獻2]特開平〇㈣⑽號公報。 銀,、、:人古1利用光此的染髮料指出含有硝酸銀和/或乳酸 醇$ S Μ乙烯硬脂基鱗等表面活性劑、十六燒醇等 丙二醇等保濕劑的膏狀或液狀之單劑型染髮料。 、可苓考〔專利文獻3]特開2〇〇2_348221號公報。 再者’尚有提案提出了下述之單劑型染髮料:在液體 石職中使用聚氧乙烯硬脂基表面活性劑,在丙二醇、 對經基苯甲酸甲1旨、純化水等水溶成分中進行乳化,進一 :混合删酸、蜂壤以製成乳狀液,在其中加入乳酸銀、梢 s夂銀氟化銀、銀的配位離子中任何一種的水溶液,以製 成乳狀液的單劑型染髮料。 將該染髮料塗佈於頭髮後,在一般的生活環境中暴露 於日光下一天後洗髮,頭髮上的顏色會呈現銅褐色之不自 然的顏色,然後,即使每天洗髮,經過20天後也未發現 頭髮染色狀況發生變化。 以上可翏考〔專利文獻4]特開2004-99502號公報。 另一方面,有提案提出一種人工曬黑劑組合物,其係 b有·(a)一羥基丙酮;(b)選自丙胺酸(a|an.me)、纈胺酸 (vaiine)、白胺酸(|eucine)、異白胺酸 r|s〇|eucine)、脯胺 7 200803906 酸(proline)、曱硫胺酸(methionine)、 ***酸 (phenylalanine) ^ 色胺酸(tryptophan)、甘胺酸(glycine)、 絲胺酸(serine)、蘇胺酸(threonine)、半胱胺酸(cysteine)、 絡胺酸(tyrosine)、天門冬酸胺(asparagine)、麩醯胺 (glutamine)、賴胺酸(|ySine)、精胺酸(a「ginine)、組胺酸 (histidine)以及上述胺基酸混合物組成的群組中之胺基酸 及其鹽類’以及(c)局部載體’該組合物的ρ η為4以下, 其顯色性得到了改善。In addition, the test [Patent Document 2] is published in the Gazette (4) (10). Silver,,,: People's ancient 1 uses the dyeing material of the light to indicate a paste or liquid containing a surfactant such as silver nitrate and/or lactate alcohol, such as surfactants such as vinyl stearyl squama, and propylene glycol such as hexadecanol. Single dose dyeing hair. Japanese Patent Laid-Open Publication No. Hei 2 No. 2-348221. Furthermore, there are proposals to propose a single-dose dyeing agent for use in a liquid stone work using a polyoxyethylene stearyl surfactant in a water-soluble component such as propylene glycol, p-benzoic acid, and purified water. Emulsifying, further: mixing acid and bee soil to form an emulsion, and adding an aqueous solution of any one of silver lactate, silver sulphide silver, and silver coordination ions to prepare an emulsion Single-dose dyeing. After the hair dye is applied to the hair, it is shampooed after being exposed to sunlight in a normal living environment for a day, and the color on the hair will be an unnatural color of copper brown, and then, even after shampooing every day, after 20 days No changes in hair coloring conditions were observed. The above is a reference to [Patent Document 4] JP-A-2004-99502. On the other hand, there is a proposal to propose an artificial tanning agent composition which has (a) monohydroxyacetone; (b) is selected from the group consisting of alanine (a|an.me), valine (vaiine), white Amine (|eucine), isoleucine r|s〇|eucine), indoleamine 7 200803906 acid (proline), methionine, phenylalanine ^tryptophan, sweet Glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, Amino acid (|ySine), arginine (a "ginine", histidine, and a mixture of the above amino acids, amino acids and salts thereof" and (c) a local carrier The composition has a ρ η of 4 or less, and its color rendering property is improved.
上述二羥基丙酮是經由與皮膚的含氮蛋白質進行反 應,而在人的皮膚上形成人工曬黑的物質,然而,該人工 曬黑劑組合物無法與毛髮的角蛋白產生反應,因此不能對 毛髮進行染色。 以上可參考〔專利文獻5]特表平9_51〇971號公報。 而目前市售之利用光能的染髮料,大致上係將毛髮染 色為稍微偏紅色的茶色,而在已針對白頭髮進行染色為目 的的情況:,現在流行的顏色是看起來較為自然的茶褐色 到灰黑色系的顏色,因此市售盡口 > 必須重複 此外,由於市售染髮料的單次著色力較弱 塗抹多次,所以對於使用者而言非常的麻煩。 【發明内容】 因此發明出一種 要的特徵在於藉 本發明人有鑑於上述染髮料的缺點, 利用光能的單劑型染髮料。 本發明利用光能的單劑型染髮料最主 8 9 200803906 由在染髮料膏基添加含銀鹽類(其中不包括函化銀),並用 胺基酸來提高染髮效果,並可藉由胺基酸(其中不包括半脱 胺酸等還原性胺基酸和甲硫胺酸等含硫胺基酸)的種類以及 =比例的不同組合,俾使得色調和色相具有一定程度的 特別地,本發明的特徵係本發明可藉由含銀鹽類(盆中 不包括鹵化銀)和驗性胺基酸的組合,而抑制以往染後毛彩 稍微偏紅的顏色,且能夠將毛髮 交 褐色系的顏色。 μ色為紅兔到命紫色或茶 進一步來說,本發明豆中一批 ^ ^ ^ T 4寸徵係尚可在所述之毕髮 料中添加有少量的二羥基丙酮。 μ 此外,本發明特徵還在於所述染髮料中配合添 減酸離子或乙基硫酸離子為反離子的陽離子型表面活性 劑,以作為染髮料膏基中所使用的表面活性劑。 者的=本^利用光能的單劑型染髮料,可不損傷使用 因:產生皮膚炎症狀。此外,本發明為單劑型 料’因此操作容易,進-步來說,本發明具有下述 ⑴將本發明㈣於毛髮後,只独日光直射3()分鐘 二:’,銀鹽類就能牢固地附著於毛髮上,顏色 …的,間較長(約2個月〜3個月),即使與永久 乐艾劑相比也毫不遜色。 ⑵能夠將白頭髮染色為適合白髮的自然色〜欠褐色 到灰黑色系的顏色。 才、 9 200803906 (3)本备明染髮料之嘗基中配合添加有特定的陽離子 型表面活性劑時,可以進一步提高該染髮料的穩 定性。 【實施方式】 本發明係藉由在一染髮料膏基中添加〇. 3 wt%〜5. 〇 wt% 之不包括鹵化銀的含銀鹽類和〇·2 wt%〜5·〇 wt%之不包栝 如半胱胺酸之還原性胺基酸和如甲硫胺酸之含硫胺基酸的 胺基酸,以獲得利用光能的單劑型染髮料。 上述不包括鹵化銀的含銀鹽類係選自於硝化銀、硫酸 銀、乳酸銀。 上述胺基酸係選自/5 -丙胺酸、羥基笨丙胺酸、4 —胺基 丁酸、DL-胺基丁酸、酪胺酸、羥脯胺酸等中性胺基酸; 麵胺、天門冬醯酸等酸性胺基酸以及精胺酸、組胺酸、 賴胺酸等鹼性胺基酸’進一步可使用牛磺酸等胺基磺酸。 較佳之胺基酸為精胺酸、組胺酸、賴胺酸等鹼性胺基 酸。 上述製劑的pH調整為2〜8。 進一步來說,上述染髮料組成尚添加5%的二 羥基丙酮(下文簡稱DHA),並將該染髮料的pH値調整為 2〜7,以製成利用光能的單劑型染髮料。 上述染髮料的pH值皆可任意調整,但下述實施例若未 加以說明之時,則係利用擰檬酸或氫氧化鈉水溶液進行調 整。 此外,本發明之染髮料尚可添加於本領域具有通常知 10 200803906 識者所知的各種添加劑, ^丄 作為保濕成分的50wt%乳酸鈉、 染髮料的穩定性 作為穩定劑的依地酸二鈉等,只要不損宝 即可。 、ΰ 上述染髮料膏基的特點如下所述: 一,的護髮素(hair condltioner)或潤髮劑(⑽ 二:se一 :毛:用產品中大量使用了硬脂基三甲基氯化銨、 %基-甲基氯化録等具有長鏈炫基鏈的陽離子型表 =劑,並使其特性得到發揮。在市售利用光能的染髮 T中也可以少量添加上述陽離子型表面活性齊卜 陽離+ 2的“(haw CreaiD)中添加有1Wt%以下的上述 ==面活性劑是無妨的,藉由在髮膏中添加這些陽 、广面活性劑與高級醇類相混合,可减少油相成分, 以提供具有塑型力(七、y卜力 適的產品。 个^頭芡沾黏不 但是’在使用含銀鹽類之利用光能的單劑型毕髮料, • c述配方時可能會産生問題。這是因為染髮料 二::中的含銀鹽類與作爲陽離子型表面活性劑之反離 光材反應産生氯化銀’該反應如同用於照相的感 霜中夹 光極其敏感,因而當含銀鹽類會緩慢地從髮 速^毛髮’且在還原固定顯色之前,在膏相中會被快 /原以銀或氧化銀等形式作爲黑色粒子析 =髮外觀表現出毛髮染黑的狀態,但由於這些黑色粒子 :洗髮劑洗掉而幾乎不殘留於毛髮上 劑型染髮料膏基中。 不週用於早 11 200803906 …所以在添加烧基三甲基氯化物類陽離子型表面活性劑 寻以氣離子(進一步以齒離子)爲反離子的陽離子型表' 性劑時,冑了不降低染髮料的染色力’其添加量明領= 限制。利用如此受到限制的添加量時’有可能在針對:髮 的柔軟性或塑型力方面不能充分地發揮性能。 ,陽Γ黑色粒子析出現象不僅在使用燒基三甲基.氯化錢 %讓子型表面活性劑時出現,也在卣離子存在時大旦从 出現。進-步而言,當所使用的含銀鹽類易溶於水中t 該現象會更快地出現。 含二:,一般熟知作爲還原劑的物質不適於添加至使用 髮劑用光能的單劑型染髮料中。這是由於若在染 硫m 1銀鹽類與抗壞血酸、亞硫酸鹽、半胱胺酸等含 氣U,、性胺基酸等的強力還原性物 間會被還原而析出$色的銀微粒,則刚類瞬 降低。 出',、、色的銀微粒,從而使其染髮能力顯著 發生銀鹽類共存的爲還原力較弱的還原性物質,則 不同,度就會根據其添加量以及保存狀態的不同而 如二^劑的狀態也會隨著時間的推移而變化。 ’由於染髮劑的染髮 # 所以即使添加的是弱還原性物推移而降低’ 用含銀_盤 、也不優於將其添加在使 地,當二、之利用光能的單劑型染髮料膏基中。進-步 佈於毛每有甲ϋ酉夂等合硫胺基酸的單劑型染髮料塗 適感。另外,才、"産生硫類的不適臭味,讓使用者產生不 %、加有5 &胺基酸的染髮料不僅不能在毛髮 12 200803906 上生成硫化銀,而且未發現其具有將毛髮染色成作爲本發 明目的的褐色到黑灰色系的作用效果。 本毛月之單劑型染髮料貧基中所使用的表面活性劑較 佳的是聚氧乙烯高級醇醚和/或以曱基硫酸離子或乙基硫 酸離子爲反離子的陽離子型表面活性劑。 上述之聚氧乙烯高級醇醚可選自於聚氧乙烯(5,5)十六 烷基醚(下文簡稱爲p〇e(5,5)十六烷基醚)、聚氧乙烯(2〇') 十六烷基醚(下文簡稱爲POE(20)十六烷基醚)、聚氧乙烯 (20)二十二烷基醚(下文簡稱爲p〇E(2〇)二十二烷基醚) 等。 上述之甲基硫酸離子或乙基硫酸離子爲反離子的陽離 子型表面活性劑可選自於乙基硫酸羊毛脂脂肪1胺丙基乙 基二甲基銨(下文簡稱爲羊毛脂衍生物季銨鹽)、甲基硫酸 羊毛脂脂肪酰胺丙基三甲基銨、乙基硫酸二十二烷基乙基 二甲基銨、甲基硫酸二十二烷基三甲基銨等。 特別是這些以乙基硫酸離子、甲基硫酸離子爲反離子 的陽離子型表面活性劑,在含銀鹽類的存在下對光也不會 過度敏感地作用,可以充分發揮作爲利用光能的單劑型染 髮料的作用。 而且,藉由添加上述特定的陽離子型表面活性劑,可 以進一步提高製劑的穩定性。 適合作爲上述陽離子型表面活性劑的乙基硫酸羊毛脂 脂肪魏》胺丙基乙基二甲基銨(下文簡稱爲羊毛脂衍生物季 銨鹽),其係由羊毛脂脂肪1胺丙基二甲基胺和二乙基硫 13 200803906 酸通過下式製造的季銨鹽。 ch3 \+ I I r-n-c2h5 |c2h5s〇4 I I CH3 \ ch3 / 上式中,R爲羊毛脂脂肪酰胺丙基殘基。The above-mentioned dihydroxyacetone is a substance which forms artificial tanning on the skin of a human by reacting with a nitrogen-containing protein of the skin. However, the artificial tanning agent composition cannot react with the keratin of the hair, and thus cannot be applied to the hair. Dyeing. The above is referred to [Patent Document 5] Japanese Patent Publication No. Hei 9-51〇971. Currently, commercially available hair dyes using light energy generally dye hair to a slightly reddish brown color, and in the case of dyeing for white hair: the color that is now popular is a natural brown color. It is necessary to repeat the color of the gray-black color, so the market is finished. In addition, since the single coloring power of the commercially available hair dye is weakly applied a plurality of times, it is very troublesome for the user. SUMMARY OF THE INVENTION Therefore, it is a feature of the invention that the present inventors have used a single-dose dyeing of light energy in view of the above-mentioned shortcomings of the hair dye. The present invention utilizes a single dose of light energy to produce a hair dye. The main product is 8 9 200803906. The silver-containing salt (which does not include the functional silver) is added to the dye base, and the amino acid is used to improve the hair dyeing effect, and the amino group can be used. Different combinations of the acid type (excluding the sulfur-containing amino acid such as a semi-deaminating acid and a thiol-containing acid such as methionine) and the ratio of the ratio, such that the color tone and the hue have a certain degree, in particular, the present invention The present invention is capable of suppressing the color which is slightly reddish in the past dyed color by the combination of the silver-containing salt (excluding silver halide in the pot) and the test amino acid, and is capable of imparting brown hair to the hair. colour. The μ color is red rabbit to life purple or tea. Further, a batch of ^ ^ ^ T 4 inch in the bean of the present invention can be added with a small amount of dihydroxyacetone in the finished product. Further, the present invention is characterized in that the hair dye is compounded with a cationic surfactant having an acid ion or an ethyl sulfate ion as a counter ion as a surfactant used in the base of the hair dye. The person's = this ^ use a single dose of light energy dyeing materials, can not damage the use of: due to the appearance of dermatitis symptoms. Further, the present invention is a single-dose type material, so that the operation is easy. In the present invention, the present invention has the following (1). After the invention (4) is applied to the hair, only the direct sunlight is 3 () minutes two: ', the silver salt can It is firmly attached to the hair, and the color is longer (about 2 months to 3 months), even if it is compared with the permanent music agent. (2) It is possible to dye white hair into a natural color suitable for white hair ~ a color that is less brown to grayish black.才, 9 200803906 (3) When the specific cationic surfactant is added to the tasting base of the prepared hair dye, the stability of the dyeing material can be further improved. [Embodiment] The present invention is made by adding 〇. 3 wt% 〜5. 〇wt% of silver-containing salts excluding silver halide and 〇·2 wt% 〜5·〇wt% A reducing amino acid such as cysteine and an amino acid containing a thioaminic acid such as methionine are not included to obtain a single-dose hair dye using light energy. The above silver-containing salts not including silver halide are selected from the group consisting of silver nitrate, silver sulfate, and silver lactate. The above amino acid is selected from the group consisting of a neutral amino acid such as /5-alanine, hydroxy azlactone, 4-aminobutyric acid, DL-aminobutyric acid, tyrosine, hydroxyproline; Acidic amino acids such as aspartic acid and basic amino acids such as arginine, histidine, and lysine may be further used as the amine sulfonic acid such as taurine. Preferred amino acids are basic amino acids such as arginine, histidine and lysine. The pH of the above preparation was adjusted to 2 to 8. Further, the above hair dye composition is further added with 5% of dihydroxyacetone (hereinafter abbreviated as DHA), and the pH of the dyeing material is adjusted to 2 to 7, to prepare a single-dose dyeing material using light energy. The pH of the above-mentioned hair dye can be arbitrarily adjusted, but the following examples are adjusted by using citric acid or an aqueous sodium hydroxide solution unless otherwise specified. Further, the hair dye of the present invention may be added to various additives known in the art and known in the art as a moisturizing ingredient, 50% by weight of sodium lactate as a moisturizing ingredient, and the stability of hair dye as a stabilizer, such as disodium edetate. As long as it does not damage the treasure. ΰ The characteristics of the above-mentioned hair dye base are as follows: 1. Hair condltioner or hair conditioner ((10) 2: se one: wool: stearyl trimethyl chloride is used in large quantities in the product. A cationic table-like agent having a long-chain stilbene chain such as ammonium or %-methyl-methyl chloride, and exhibiting its characteristics. The above-mentioned cationic surface active can also be added in a small amount in commercially available hair dyed T. It is possible to add 1 wt% or less of the above-mentioned == surfactant to the "haw CreaiD" of Qi Buyang + 2, by adding these cation, wide-surface active agents and higher alcohols to the cream. It can reduce the oil phase composition to provide a product with a molding force (seven, y 力 力 。 个 个 个 个 芡 芡 芡 芡 芡 芡 芡 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在This may cause problems. This is because the silver-containing salt in the hair dye 2:: reacts with the counter-reflecting material as a cationic surfactant to produce silver chloride. The reaction is like a photographic cream for photographic exposure. Extremely sensitive, so when silver-containing salts will slowly slow down from the hair And before the reduction and fixed color development, in the paste phase, it will be as a black particle in the form of silver or silver oxide, and the appearance will show blackness of the hair, but since these black particles: shampoo is washed off It does not remain in the hair-based dyeing base of the hair. It is not used in the early 11 200803906 ... so the addition of the trimethyl chloride-based cationic surfactant to find the gas ion (further with the tooth ion) as the opposite When the ionic cationic type of agent is used, it does not reduce the dyeing power of the dyeing material. The amount of addition is clearly limited. When using such a limited amount of addition, it is possible to target the softness or molding force of the hair. The aspect can not fully exert its performance. The appearance of black particles in Yangshuo appears not only when using trimethyl methacrylate, chlorinated money, but also when it is used in the presence of cerium ions. In other words, when the silver-containing salt used is easily soluble in water, this phenomenon will occur more quickly. Containing two: It is generally known that a substance as a reducing agent is not suitable for addition to a single-dose type hair dye using light energy for hair spray. Medium. This When the sulfur-reactive m 1 silver salt is reduced with a strong reducing substance such as ascorbic acid, sulfite or cysteine, and a strong reducing substance such as an amino acid, and silver particles of $ color are precipitated, The genus is instantaneously reduced. The silver particles of ',, and color, so that the hair dyeing ability is remarkable, the silver salt coexisting is a reducing substance with weak reducing power, and the degree is different depending on the amount of addition and the state of preservation. The state of the two agents will change with the passage of time. 'Because of the dyeing of the hair dye #, even if the addition of weakly reducing substances is reduced, the use of silver-containing plates is not preferable. It is added to the ground, and in the case of a single-dose dyeing base using light energy, it is applied to a single-dose hair dye having a thiol-like acid such as formazan. In addition, only, "produces the unpleasant odor of sulfur, so that users can produce non-%, with 5 & amino acid dyeing materials not only can not produce silver sulfide on hair 12 200803906, and it has not been found to have hair The effect of the brown to black gray color which is the object of the present invention is dyed. The surfactant used in the single-dose dyeing base of the present month is preferably a polyoxyethylene higher alcohol ether and/or a cationic surfactant having a mercaptosulfate ion or an ethylsulfide ion as a counter ion. The above polyoxyethylene higher alcohol ether may be selected from polyoxyethylene (5,5) cetyl ether (hereinafter abbreviated as p〇e (5,5) cetyl ether), polyoxyethylene (2〇) ') Cetyl ether (hereinafter abbreviated as POE (20) cetyl ether), polyoxyethylene (20) behenyl ether (hereinafter abbreviated as p〇E (2〇) behenyl Ether) and so on. The cationic surfactant having the above methyl sulfate ion or ethyl sulfate ion as a counter ion may be selected from the group consisting of ethyl sulphate lanolin fat 1 amine propyl ethyl dimethyl ammonium (hereinafter referred to as lanolin derivative quaternary ammonium) Salt), methyl sulphate lanolin fatty amide propyl trimethyl ammonium, ethyl sulphate behenyl ethyl dimethyl ammonium, methyl sulphate behenyl trimethyl ammonium. In particular, these cationic surfactants having an ethyl sulphate ion and a methyl sulphate ion as a counter ion do not act too sensitively on light in the presence of a silver-containing salt, and can sufficiently exhibit a single use as light energy. The role of the dosage form of dyeing hair. Further, by adding the above specific cationic surfactant, the stability of the preparation can be further improved. Ethyl propyl sulphate, which is suitable as the above cationic surfactant, is propyl propyl dimethyl ammonium (hereinafter referred to as lanolin derivative quaternary ammonium salt), which is derived from lanolin fat 1 amine propyl Methylamine and diethylsulfide 13 200803906 The quaternary ammonium salt produced by the following formula. Ch3 \+ I I r-n-c2h5 |c2h5s〇4 I I CH3 \ ch3 / In the above formula, R is a lanolin fatty amide propyl residue.
R — N CH ‘ + (C2H5) 2S〇‘R — N CH ‘ + (C2H5) 2S〇 ‘
[貫施例1 ] 實施例1中,使用下述染髮料膏基A。 [染髮料膏基A] 6. 7重量% 8. 3重量% 1. 7重量% 6. 8重量% 0. 8重量% 1. 1重量% 1. 1重量% 環狀矽酮 甲基苯基梦顚) 西蒙得木油(jojoba 〇ii) 十六烷醇 親油性硬脂酸單甘油酯 ?〇£(5,5)十六烧基醚 JPOE (20)t六烷基醚 用純化水製成1〇〇 wt% 该染髮料膏基A爲柔軟的乳白色的膏狀物。 實施例1所示範的製劑中,使用上述染髮料膏基A, 添加硝酸銀作爲含銀鹽類,並添加組胺酸作爲胺基酸。各 成分添加量的單位爲克(g)。[Example 1] In Example 1, the following hair dye base A was used. [dyeing paste base A] 6. 7 wt% 8. 3 wt% 1. 7 wt% 6. 8 wt% 0. 8 wt% 1. 1 wt% 1. 1 wt% cyclic anthrone methylphenyl Nightmare) Jojoba oil (jojoba 〇ii) Cetyl alcohol lipophilic stearic acid monoglyceride? ( £ (5,5) hexadecyl ether JPOE (20) t hexaalkyl ether made with purified water 1% by weight The hair dye base A is a soft milky white paste. In the preparation exemplified in Example 1, the above-mentioned hair dye base A was used, silver nitrate was added as a silver-containing salt, and histidine was added as an amino acid. The unit of the amount of each component added is gram (g).
14 200803906 硝酸銀 1.5 組胺酸 1.0 DHA PH 3.6 1 · 5 1. 5 0· 4 3· 4 — 用純化水製成l〇〇g。 [製劑的穩定性試驗] 穩定性試驗以在45Ό的負荷溫度下經過1周後的狀辦 進行判定。 〜 [髮束的染色試驗] 染色試驗使用市售的1束lg的髮束,該髮束爲用於染 髮試驗的白色人髮(毛束屋製)。在該髮束上塗布i次約 之利用光能的染髮料膏劑,在晴天太陽下透過南側窗玻璃 照射日光1次,照射時間2小時。此外,」日丄次在室内 螢光燈(約6〇cm)下放置6小時。 然後,用洗髮劑充分洗滌,漂洗後,乾燥髮束。 重覆該操作3次。 夕j述處方Νο·ι製劑最初的顏色爲白色,隨著時間的推 私不著色而壬穩定狀態。其在髮束染色試驗中的結果為: 髮束的顏色爲茶色。 ,處:I0.2製劑爲不添加胺基酸的對照組,製劑最初的 顏色爲欠命色,隨著時間的推移稍微著色成茶色,是 穩定狀態。复Λs人丄 /、在木色试驗中的結果為:髮束的顏色爲紅芊 色’染髮力較弱。 处方No. 3製劑同樣爲對照組,雖然製劑最初的顏色爲 15 ζυυδυ^^υο 白色’但是隨著時 其在染色試驗中的鈐、推移變成灰色,是呈不穩定狀態。 的茶色,染髮力較弱1果為:髮束的顏色爲帶有較深的紅色 [貫施例2 ] 實施例2所示範 添加硝酸銀作爲含I的衣劑中,使用上述染髮料膏基Α, S銀鹽類,添加羥脯胺酸作爲胺基酸。14 200803906 Silver nitrate 1.5 Histamine 1.0 DHA PH 3.6 1 · 5 1. 5 0· 4 3· 4 — Made with purified water. [Stability test of the preparation] The stability test was carried out after one week passed at a load temperature of 45 Torr. ~ [Staining test of hair bundle] For the dyeing test, a commercially available bundle of 1 lg hair bundles for white hair (hair bundle house) for dyeing test was used. A hair dye paste using light energy was applied to the hair bundle for about 1 time, and the sunlight was irradiated once through the south side window glass in a sunny day, and the irradiation time was 2 hours. In addition, the Japanese time is placed under an indoor fluorescent lamp (about 6 〇 cm) for 6 hours. Then, it is thoroughly washed with a shampoo, and after rinsing, the hair bundle is dried. Repeat this operation 3 times. The first color of the prescription Νο·ι preparation is white, and the state of stability is not colored as time passes. The result of the hair bundle dyeing test is: The color of the hair bundle is brown. At the same time, the I0.2 preparation was a control group in which no amino acid was added, and the initial color of the preparation was a dull color, which was slightly colored to brown with time and was in a stable state. The result of the Λ 丄 、 /, in the wood color test is: the color of the hair bundle is red ’ color dyeing power is weak. The formulation of Formulation No. 3 was also a control group, and although the initial color of the preparation was 15 ζυυδυ^^υο white', the sputum in the dyeing test turned gray, and it was unstable. The color of the brown hair is weaker. The fruit is: the color of the hair bundle is dark with a red color. [Example 2] The silver nitrate is added as the coating agent containing I in Example 2, and the above-mentioned hair dye base is used. , S silver salt, adding hydroxyproline as the amino acid.
處方 膏基A 硝酸銀 經脯胺酸 DHAPrescription cream base A silver nitrate by lysine DHA
No.4(g) 70. 0 1. 5 1.0 將汕 1-- 馬4· 〇,用純化水製成l〇〇g 移不2處t:。?製劑最初的顏色爲白色’隨著時間的推 走的結p %定狀態。其在染色試驗中的結果為:髮 、多、色爲帶有較深的紅色的紅茶色,是鮮豔的色調。 [實施例3] π 貝轭例3所示範的製劑中使用上述染髮料膏基a,添 加爪I銀作爲含銀鹽類,而所添加的胺基酸有所改變。各 成分添加量單位的爲克(g)。No.4(g) 70. 0 1. 5 1.0 汕 1-- Horse 4· 〇, made with purified water l〇〇g Moved not 2 places t:. ? The initial color of the formulation was white as the state of the knot pushed away over time. The result in the dyeing test is: hair, color, and color are reddish brown with a deep red color, which is a vivid color tone. [Example 3] The above-mentioned hair dye base a was used in the formulation exemplified in Example 3 of π yoke, and the silver of the claw I was added as the silver-containing salt, and the amino acid to be added was changed. The unit of addition of each component is gram (g).
No^6 70. 〇 N o . 5 貧基A 70.0 16 200803906 硫酸銀 1. 5 胺基酸 組胺酸1. 0 DHA 0· 4 保濕成分: 10· 0 5 0 %乳酸納 pH 4. 5 精胺酸0. 4 #胺酸0. 4 用純化水製成1 〇 〇 g。 上述處方No· 5製劑最初的顏色爲白色,隨著時間的推 移稍微變成灰色。其在染色試驗中的結果為·每 爻東的顏色 爲茶色。 上述處方No. 6製劑最初的顏色爲白色,隨著時間的推 移變成極微的桃紅色。其在染色試驗中的結果為:^束的 顏色爲帶有較深的紅色的紅茶色,是鮮豔的色調。及 [實施例4 ] 貝施例4所不耗之對照組的製劑中,使用上述染髮料 賞基 A ’改變含銀gg释$ ==3銀1々和胺基酸,並進一步添加有硬脂基 一甲基氣化錢。各成分胃,σ 风刀泰加量的單位爲克(g)。 ____處方__ 膏基A 含銀鹽類 胺基酸 硬脂基三甲基氯化銨 __Ν〇^__No. 8 70. 0 70. 0 硝酸銀1. 0 溴化銀0. 8 組胺酸1. 0 谷胺酸1. 0 17 200803906No^6 70. 〇N o . 5 Lean base A 70.0 16 200803906 Silver sulfate 1. 5 Amino acid histidine 1. 0 DHA 0· 4 Moisturizing ingredients: 10· 0 5 0 % Lactic acid pH 4. 5 fine Amino acid 0. 4 #amine acid 0. 4 Made with purified water to make 1 〇〇g. The initial color of the above-mentioned prescription No. 5 preparation was white, and it became slightly grayish with time. The result in the dyeing test was that the color of each 爻 East was brown. The formulation of the above-mentioned Formulation No. 6 formulation was white in color and became extremely pink as time progressed. The result in the dyeing test is that the color of the bundle is a reddish brown with a dark red color, which is a vivid hue. And [Example 4] In the preparation of the control group which was not consumed by the application of the above-mentioned Example 4, the above-mentioned hair dyed base A ' was used to change the silver-containing gg release $==3 silver 1 々 and the amino acid, and further added with a hard The fat-based monomethylated gas. For each component of the stomach, the unit of the amount of σ wind knife is gram (g). ____ prescription __ paste base A containing silver salt amino acid stearyl trimethyl ammonium chloride __ Ν〇 ^ __ No. 8 70. 0 70. 0 silver nitrate 1. 0 silver bromide 0. 8 histidine 1. 0 glutamic acid 1. 0 17 200803906
DHADHA
用純化水製成lOOg。 上逐慝方Ν0· ί的聚劑是添加了 ,社 > 』更月日基二甲基氯化銨 (其爲具有氣離子作爲反離子的陽離子型表面活性劑)的對100 g of purified water was used. The granules of the 慝 慝 Ν · · 是 是 是 添加 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社 社
'm然製劑最初的顔色爲4,但是隨著時間的推移 顯著著色。其在染色試驗中的結果為:染髮力顯著降低。夕 上述處# No. 8的製劑是添加了具有溴離子的含銀趟類 的對照組,製劑最初的顏色爲白色,隨著時間的推移 無變化。其在染色試驗中的結果為:即使受日光照 也完全沒有變色,並且對毛髮也沒有著色。 Θ [實施例5] 實施例5中使用下述染髮料膏基b。 [染髮料膏基B ] 1· 5g 1 · Og 1. 2g 4. Og 0· 4g 0· 6g 0· 6g 〇. 8g 環狀矽酮 角鯊烧(squalan) 西蒙得木油 十六烷醇 親油性硬脂酸單甘油酯 Ρ0Ε (5,5)十六烧基醚 Ρ0Ε (20)二十二烷基醚 銨鹽(50%溶液2 用純化水製成70g。 該染髮料膏基B是黏彈性猶高於上述染髮料膏基A的乳白色的良狀物 18 200803906 貫施例5所示範的製劑中,使用上述染髮料膏基b, 添加硝酸銀作爲含銀鹽類,又添加組胺酸作爲胺基酸。各 成分添加量的單位爲克。The initial color of the 'm' formulation was 4, but it was significantly colored over time. The result in the dyeing test was that the hair dyeing power was significantly reduced. The preparation of the above No. 8 was a control group containing a silver-containing quinone having a bromide ion, and the initial color of the preparation was white, and there was no change with time. The result in the dyeing test was that there was no discoloration at all even under the illumination of the sun, and there was no coloration on the hair. Θ [Example 5] The following hair dye base b was used in Example 5. [dyeing cream base B] 1· 5g 1 · Og 1. 2g 4. Og 0· 4g 0· 6g 0· 6g 〇. 8g 矽 矽 角 角 角 西 西 西 西 西 西 西 西 西 西 西 西 西 西 西 西 西Oily stearic acid monoglyceride Ρ0Ε (5,5) hexadecyl ether Ρ0Ε (20) behenyl ether ammonium salt (50% solution 2 made with purified water 70g. The hair dye base B is sticky The elasticity is higher than the milky white good of the above-mentioned hair dye base A. 200803906 In the formulation exemplified in Example 5, the above-mentioned hair dye base b is used, silver nitrate is added as a silver-containing salt, and histidine is added as a Amino acid. The unit of the amount of each component added is gram.
處方 膏基B 硝酸銀Prescription cream base B silver nitrate
組胺酸DHApHHistidine DHApH
70. 070. 0
70· 0 3. 0 70. 0 3. 0 用純化水製成l〇〇g70· 0 3. 0 70. 0 3. 0 made with purified water l〇〇g
上述處方No. 9的製劑最初的顏色爲極淺的茶色,隨著 時間的推移變务sβ ^ γ文化馬、成余色。其在染色試驗中的結果為··髮 束的顏色爲深茶褐色。 處方Νοβ 1 〇 的顏色爲白色, 試驗中的結果為 染髮力較弱。 的製劑爲未添加胺基酸的對照組,其最初 但是隨著時間的推移變成灰色。其在染色 •髮束的顏色爲帶有較深的紅色的茶色, 1处方N〇.U的製劑最初的顏色爲白 &隹移(10天)變成撥色。其在染色試驗中的 的顏色爲濃以。其適心商業用途。 :方No.l2的製劑是ρΗ超過7.0施 =二進行調整,使其最初的顏色爲灰 Λ…、色,其係呈現不穩定狀態。其在 ,隨著時間 果為··髮束 ,以碳酸氫 ’但疋其立 色試驗中的 19 200803906 結果:對於髮束幾乎無染髮力。 [實施例6] 實施例6 所示範的製劑中,使用上述染髮料膏基B, 添加硝酸銀作 爲含銀鹽類 ’添加精胺酸作爲胺基酸。各成 为添加量的單位爲克(g)。 處方 No. 13 No. 14 No. 15 No 16 膏基B 70. 0 70. 〇 70. 〇 70. 0 硝酸銀 1.5 1. 5 1· 5 1_ 5 精胺酸 2. 0 2. 0 2· 0 2. 0 DHA 〇· 1 0· 1 穩定劑 • 依地酸二鈉 0· 1 PH ----— 6. 0 3· 1 3^8 7· 8 用純化水製成l〇〇g。 ——--—— 上述處方No· 13的製劑最初的顏色爲白色,隨著時間 的推移無變化。其在染色試驗中的結果:冑束的顏色爲册 有較深紅色的紫色。 上述處方No· 14的製劑最初的顏色爲白色,隨著時間 的推私不產生著色現象。其在染色試驗中的结 · ^ 丄也丈M > 、不两·髮束 的顔色爲茶紫色。 處方Ν ο · 15的製劑最初的顏色爲白色,隨菩士 专吋間的推 私不著色,是呈穩定現象。其在染色試驗中的結 ^ 束的顏色爲帶有紫色的茶色。 ^ ”、、.髮 20 200803906 ☆地方N〇· 16的製劑爲pH超過7. 0的對 、 爲茶色,然德制▲ 、組’最初著色 …、後製劑的著色顯著。其在染色 巴 雖然髮束的声5 & 6 —么 匕式驗中的結果為: 低。 的推移染色力降 [貫施例7 ] ““"所示範的製劑中,使用上述 添加硝酸銀作致人鋁趟相^ ^ ^^ 卞反抖㈢基Β, 乍爲s銀鹽類,添加酪月女酸作 分添加量的單位爲克(g)。 ^絲各成The initial color of the preparation of the above prescription No. 9 is extremely light brown, and the sβ ^ γ culture horse is changed over time to form a residual color. The result of the dyeing test was that the color of the hair bundle was dark brown. The color of the prescription Νοβ 1 〇 is white, and the result of the test is that the hair dyeing power is weak. The formulation was a control group without the addition of amino acids, which initially turned grey over time. It is dyed • The color of the hair bundle is brown with a darker red color, and the initial color of the formulation of the prescription N〇.U is white & shift (10 days) to become a color. Its color in the dyeing test is concentrated. It is suitable for commercial use. The preparation of the square No.l2 is adjusted such that the initial color is ash..., color, and the system exhibits an unstable state. It is, in the case of time, the hair bundle, with hydrogen carbonate ‘but in the test of its color 19 200803906 results: almost no hair dyeing for the hair bundle. [Example 6] In the exemplified formulation of Example 6, the above-mentioned hair dye base B was used, and silver nitrate was added as a silver salt-containing arginine as an amino acid. The unit of each added amount is gram (g). Formulation No. 13 No. 14 No. 15 No 16 Paste base B 70. 0 70. 〇70. 〇70. 0 Silver nitrate 1.5 1. 5 1· 5 1_ 5 arginine 2. 0 2. 0 2· 0 2 0 DHA 〇· 1 0· 1 Stabilizer • Disodium edetate 0· 1 PH ----— 6. 0 3· 1 3^8 7· 8 Made of purified water to make l〇〇g. ———————— The formulation of the above prescription No. 13 is initially white in color and does not change over time. The result of the dyeing test: the color of the sputum is a dark red purple. The initial color of the formulation of the above-mentioned prescription No. 14 was white, and no coloration occurred with the push of time. Its color in the dyeing test is ^ ^ 丄 丈 M >, the color of the hair bundle is tea purple. The initial color of the prescription ο ο 15 is white, which is stable with the coloring of the priests. The color of the knot in the dyeing test was a purpleish brown color. ^ ",,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The results of the hair bundle 5 & 6 - 匕 匕 为 为 为 低 低 低 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色 染色Phase ^ ^ ^^ 卞 卞 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (
No. 18 70. 1. 5 2. 0 T基B 硝酸銀 酪胺酸No. 18 70. 1. 5 2. 0 T-based B silver nitrate tyrosine
DHADHA
用純化水製成l〇〇g 上述處方Ν〇· 17的 製劑最初的顏 的推移變成淡茶色。其在一中 色爲茶色。 ~ I的顏 上述處方m的製劑最初的顏色爲白色, 的推移緩慢變成茶色。其在染色試驗:間 顏色爲茶色。 的'、。果為.髮東的 [實施例8] 實施例δ所示範的製劑中,使用上述染髮料膏基b, 200803906 添加硝酸銀作爲含銀鴎 & | 4,添加/3 -丙胺酸或羥基*** 酸作爲胺基酸。夂成八a 成刀的添加量的單位爲克(g)。 INO. 19 Ί"基B 硝酸銀 胺基酸 DHA 用純化水 70. 〇 1.5 羥基笨丙胺酸0. 1. 2 4. 6 召—丙胺酸2, 1. 0 久5 1 0 Og 上述處方Ν ο · 1 9的盤南丨县、n — „ 妁衣剤取初的顏色爲白色,隨著時間 的推移變成灰色。其在毕备4认a ΤΠ 萃f 、在木色武驗中的結果:髮束的顏色爲 上述處方Νο·20的製劑良妻夭上丄 劑最初的顏♦致占念 川馬未添加硝酸銀的對照組,製 初的顏色爲白色,隨著時The original color of the preparation of the above formula Ν〇·17 was made into a pale brown color. It is brown in a medium color. The color of the preparation of the above prescription m is white, and the transition slowly turns into brown. It is in the dyeing test: the color is brown. of',. [Embodiment 8] In the formulation exemplified in Example δ, the above-mentioned hair dye base b, 200803906 was used to add silver nitrate as silver-containing strontium & 4, and /3-alanine or hydroxyphenylalanine was added. As an amino acid. The unit of the addition amount of the knives into eight knives is gram (g). INO. 19 Ί"Base B Silver nitrate amino acid DHA with purified water 70. 〇1.5 Hydroxy albendine 0. 1. 2 4. 6 Calling-alanine 2, 1. 0 Long 5 1 0 Og The above prescription Ν ο · 1 9 of Pannan County, n — „ The color of the 妁 剤 剤 白色 白色 白色 , , , , , , , 剤 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The color of the bundle is the preparation of the above prescription Νο·20, the first wife of the 良 夭 夭 丄 ♦ ♦ 致 致 念 念 念 念 念 马 马 马 马 马 马 念 念 念 念 念 念 念 念 念 念 念 念
古S人丄 了间的推移無變化。其在染多 y人 交束處理3次也不著色。這表明若 不存在含銀鹽類,則利用鞍基 「― 艾丞馱和DHA不能染髮。 [貫施例9 ] 中,使用上述染髮料膏基B, 添加胺基丁酸作爲胺基酸。各 實施例9所示範的製劑 添加硝酸銀作爲含銀鹽類, 成分添加量的單位爲克(g)。There was no change in the progress of the ancient S people. It is not colored when it is dyed 3 times. This indicates that if silver-containing salts are not present, the saddle-based "- Ai and DHA cannot be used for hair dyeing. [In Example 9], the above-mentioned hair dye base B was used, and aminobutyric acid was added as an amino acid. Each of the preparations exemplified in Example 9 was added with silver nitrate as a silver-containing salt, and the unit of the component addition amount was gram (g).
22 200803906 硝酸銀 胺基酸 2. DHA ! PH 上 用純化水製成100g 1. 5 1· ο DL-胺基丁酸4-胺基丁酸4_胺基丁酸 1· 0 0,2 5. 1. 1. 5. 上述處方Μο·21的製劑最初的顏色爲白色 的推私不發生變色。其在染色試驗中的結 色爲紅色。 ^ 上述處方Νο·22的製劑最初的顏色爲白 的推移稍微變成茶色。 其在染色試驗中的結果為··髮 茶色。 交果的顏色爲稍帶紅色的 ν処方No. 23的製劑爲未添力口石肖酸 初的顏色爲白备岐# β文銀的對照組,最 '、、、色,酼著時間的推移不變色。Α在a $ 中的結果為:欠巴其在染色试驗 吏對犮束處理3次也不著多。γ # 一 料中若π左++ 〜卜嘗巴。沒表不染髮 寸甲右不存在有含銀 义 不能染髮的。 則早早八利用胺基酸和ΜΑ是 [實施例10J 所六力實:::10所示範的製劑中’使用上述染髮料膏基Β, 所添加的含銀鹽類和胺 位爲克(g)。 谷成刀添加置的單 一處方 No· 24 No.25 隨著時間 髮束的顏 隨著時間22 200803906 Silver nitrate amino acid 2. DHA ! PH made with purified water 100g 1. 5 1· ο DL-aminobutyric acid 4-aminobutyric acid 4_aminobutyric acid 1· 0 0,2 5. 1. 1. 5. The formulation of the above prescription Μο·21 is initially white in color and does not change color. Its color in the dyeing test was red. ^ The initial color of the preparation of the above prescription Νο.22 is slightly changed to brown. The result in the dyeing test was · browning. The color of the fruit of the fruit is slightly reddish. The formulation of the prescription No. 23 is the control group of the unwashed stone. The color of the initial color is white 岐## 文 文, the most ',,, color, 酼 时间 时间 不Discoloration. The result of Α in a $ is: owing it to the dyeing test 吏 and not treating the 犮 bundle 3 times. γ # 一料 If π left ++ ~ Bu taste the bar. No table does not dye the hair. There is no silver in the right, there is no silver. Then, the use of the amino acid and hydrazine early is [Example 10J, Liu Lishi::10, the formulation of the demonstration] uses the above-mentioned hair dye base, and the added silver salt and amine are gram (g ). A single prescription for the addition of Gu Chengdao No. 24 No.25 With the time of hair, with time
膏基B 70. 70. 23 200803906Cream base B 70. 70. 23 200803906
含銀鹽類 胺基酸 DHA 硝酸銀1. 5 乳酸銀4. 〇 谷胺酸2 · 0 組胺酸1. 〇Silver-containing salt Amino acid DHA Silver nitrate 1. 5 Silver lactate 4. 谷 Glutamic acid 2 · 0 Histidine 1. 〇
用純化水製成l〇〇g。 述處方No. 24的製劑最初的顏色爲白色,隨著時 的推移欒忠命A u ^ ^ 取又色。其在染色試驗中的結果為:髮束的顏备 _ 爲稍帶紅色的茶色。 、 述處方No· 25的製劑最初的顏色爲白色,隨著時 的推移不著色。 其在染色試驗中的結果為:髮束的顏色爲稍紅 茶色。 [貫施例11 ] 、貫施例11所示範的製劑中,使用上述染髮料膏基B, "肖I銀作爲含銀鹽類,所添加的胺基酸有所變化。各 _ 成分添加量的單位爲克(g)。Made with purified water to make l〇〇g. The initial color of the preparation of the prescription No. 24 was white, and the loyalty A u ^ ^ was taken again as time passed. The result in the dyeing test is that the hair bundle _ is a slightly reddish brown. The initial color of the preparation of the prescription No. 25 was white, and it was not colored as time passed. The result in the dyeing test was that the color of the hair bundle was slightly reddish brown. [Example 11] In the preparations exemplified in Example 11, the above-mentioned hair dye base B, "Shaw I silver was used as the silver-containing salt, and the added amino acid was changed. The unit of each _ component addition amount is gram (g).
No. 26 No· 27 膏基B 70. 0 70.0 硝酸銀 2. 0 1. 5 胺基酸 組胺酸2. 0 精胺酸1. 0 0 -丙胺酸1. 0 添加劑 50%乳酸鈉10. 0 依地酸二納〇 . 1 PH ^-_ 4. 8 3. 1 24 200803906 用純化水製成100g。 上述處方No· 26的擎匈 的顏色爲白色,隨著時^ ’用乳酸調整pH。製劑最初 的結果為:髮束的顏色爲:::不著色。其在染色試驗中 的推移ΐΐ: 27的製劑最初的顏色爲白色’隨著時間 在木色忒驗中的結果為:髮束的顏色爲 [實施例12] 貝鉍例12所示範的製料,使用上 «加的含銀鹽類和胺基酸有所變化,將 刀添加s的單位爲克(g)。 成 處方 膏基 含銀鹽類 胺基酸No. 26 No. 27 Cream base B 70. 0 70.0 Silver nitrate 2. 0 1. 5 Amino acid histidine 2. 0 arginine 1. 0 0 - alanine 1. 0 Additive 50% sodium lactate 10. 0 Dibenzopyrene. 1 PH ^-_ 4. 8 3. 1 24 200803906 100 g of purified water. The color of the above-mentioned prescription No. 26 is white, and the pH is adjusted with lactic acid as time goes by. The initial result of the formulation was: the color of the hair bundle was ::: not colored. In the dyeing test, the initial color of the formulation of ΐΐ: 27 is white'. The result of the wood color test over time is: the color of the hair bundle is [Example 12] The preparation of the sample shown in Example 12 , using the addition of the silver-containing salt and the amino acid, the unit of adding s to the knife is gram (g). Formulation cream base silver salt amino acid
No· 28 70. 硝酸銀1. 0 牛續酸2. 0No. 28 70. Silver nitrate 1. 0 bovine acid 2. 0
No. 29___^ 70. 〇No. 29___^ 70. 〇
PH 6· 5 硫酸銀0. 5 賴胺酸1. 6 組胺酸1. 〇 7· 7 用純化水製成1〇〇g。 ^ 上述處方Ν〇· 28的製劑最初的顏色爲白色,隨著時間 的推移不著色。 曰 /、在^色武驗中的結果為:髮束的顏色爲帶有極微的 紅色的深茶色。 上述處方No. 29的製劑最初的顏色爲白色,隨著時間 25 200803906 的推移不著色。 其在染色試驗中的έ士要炎 Τ的、、、口果為:髮束的顏色 [實施例13 ] 馬“、、余色。 只施例13所示範的製劑 稍微調整含銀鹽類的量, 、又枓I基β, 里亚改變ΡΗ,進行添如…、 加量的單位爲克(g)。 ’、、。各成分添PH 6· 5 Silver sulfate 0.5 lysine 1. 6 Histamine 1. 〇 7· 7 Made of purified water to make 1 〇〇g. ^ The formulation of the above formulation Ν〇·28 is initially white in color and does not color over time.曰 /, in the color test, the result is: the color of the hair bundle is a dark brown with a very slight red color. The formulation of the above-mentioned Formula No. 29 was originally white in color and did not color as the time 25 200803906 progressed. The gentleman in the dyeing test is inflammatory, and the mouth is: the color of the hair bundle [Example 13] The horse ", the remaining color. Only the formulation exemplified in Example 13 slightly adjusts the silver salt-containing Quantity, and 枓I base β, ria change ΡΗ, add as..., add unit is gram (g). ',,.
用純化水製成100g 劑的染色試驗結果為:髮束的顏 上述處方No· 30的製 色爲紅茶色。 上述處方汉〇 幾乎未染 色 • 、衣蜊的染色試驗結果為 色 上述處方Ν°·32的製劑的染色試驗結果為 幾乎未染 [實施例14 ] ^施例14所示範的製劑中,使用上 调尚含銀鹽類的詈推 交科曷基B, ⑷。 〜”各成分添加量的單位爲克 26 200803906 處方 膏基B 硝酸銀 精胺酸 DHA 座 用純化水製成l〇〇g。 上述處方N〇.33的製劑的染色試驗結果為 色爲紅紫色。 上述處方Ν〇·34的製劑的染色試驗結果為 色爲紅紫色。 [實施例15] 實施例15所示範的製劑中,使用上述染髮料春 使含銀鹽類的量愷定,改變胺基酸的量和pH進一广 各成分的添加量的單位爲克(g)。 力 No· 36 No· 37 No.js 70. 〇 1 · 5 0· 5 〇. 1 3· 1The result of the dyeing test of 100 g of the purified water was as follows: the color of the hair bundle The color of the above prescription No. 30 was a brownish color. The above-mentioned prescription Han dynasty is hardly dyed. The result of the dyeing test of the clothing is coloring. The result of the dyeing test of the above formulation Ν°·32 is almost undyed [Example 14] ^The formulation demonstrated in Example 14 is used up. The silver salt-containing 詈 詈 曷 曷 曷 , , B, (4). ~" The unit of each component added amount is gram 26 200803906 Prescription cream base B Silver nitrate arginine DHA seat is made of purified water. The dyeing test result of the above prescription N〇.33 is reddish purple. The result of the dyeing test of the preparation of the above-mentioned prescription Ν〇·34 was reddish purple. [Example 15] In the preparation exemplified in Example 15, the amount of the silver-containing salt was determined by using the above-mentioned hair dye spring, and the amine group was changed. The amount of the acid and the amount of the pH added to each component are in grams (g). Force No· 36 No· 37 No.js 70. 〇1 · 5 0· 5 〇. 1 3· 1
No· 33 __No·34 70· 0 70. 〇 4. 0 4· 0 4. 0 2. 0 0· 5 0.1 2, 7 5· 3 髮束的顧 髮束的No· 33 __No·34 70· 0 70. 〇 4. 0 4· 0 4. 0 2. 0 0· 5 0.1 2, 7 5· 3 Hair bundles
用純化水製成1 〇 〇 g 上述處方No· 35的製劑的染色試驗結果為·每土1 〇 〇 g with purified water The dyeing test result of the above prescription No. 35 is · per soil
丈束的顏 27 200803906 色爲茶紫色。 上述處方No· 36的製劑的染色試驗結果為:髮束的顏 色爲茶色。 〃 上遂處方No· 37的製劑的染色試驗結果為:彩、 色爲稍帶紫色的紅色" 上述處方 爲紅色。 Ν〇· 38製劑的染色試驗結果為:髮束的顏色Yan Yan 27 200803906 The color is tea purple. As a result of the dyeing test of the preparation of the above-mentioned prescription No. 36, the color of the hair bundle was brown.染色 The dyeing test results for the preparation of the upper prescription No. 37 are: color, color is slightly purpleish red " The above prescription is red. The dyeing test results of the Ν〇·38 preparation are: the color of the hair bundle
上述處方No· 39製劑的染色試驗結果為:髮束的顏 爲稱帶紫色的紅色。 [實施例1 6 ] 貫施例1 6所示範的製劑中,使用上述染髮料膏基b, 針對DHA添加或不添加含銀鹽類並改變胺基酸進行混合。 各成分添加量的單位爲克(g)。 ___處方 No· 40 No. 41 __No. 42 T基B 70. 0 70. 0 70. 0 硝酸銀 1.0 胺基酸 4-胺基丁酸 4-胺基丁酸 經基*** 0. 5 0. 2 酸0· 2 DHA 0· 4 0. 4 1. 2 _PH 5. 7 5. 8 4. 6 用純化水製成100g。 上述處方 No. 40製劑 最初的顏色爲白色 ,隨著時間的 推移變成茶色。 28 200803906 染色試驗結果為:髮束的顏 ,^ . XT 、已局稍帶紅色的茶多 上述處方No· 41的製劑是無 ,、色。 試驗結果為··不著色。 、’里痛的對照組,染色 上述處方Na42 不著色。 L對照組,祕試驗結果為: [實施例17] 實施例17所示範的製劑The result of the dyeing test of the above-mentioned prescription No. 39 preparation was that the hair of the hair bundle was reddish purple. [Example 1 6] In the preparation exemplified in Example 16, the above-mentioned hair dye base b was used, and the silver salt was added or not added to DHA and the amino acid was changed for mixing. The unit of the amount of each component added is gram (g). ___Prescription No. 40 No. 41 __No. 42 T-based B 70. 0 70. 0 70. 0 Silver nitrate 1.0 Amino acid 4-aminobutyric acid 4-aminobutyric acid via amphetamine 0. 5 0. 2 Acid 0· 2 DHA 0· 4 0. 4 1. 2 _PH 5. 7 5. 8 4. 6 100 g of purified water. The above prescription No. 40 preparation was originally white in color and turned brown as time passed. 28 200803906 The result of the dyeing test is: the hair of the hair bundle, ^. XT, the tea that has been slightly reddish. The preparation of the above prescription No. 41 is no, color. The test result is that it is not colored. In the control group of 'the pain, the above prescription Na42 was not colored. L control group, the results of the secret test were: [Example 17] The formulation exemplified in Example 17
⑴丁 便用上述染髮料膏農R 添加胺基酸和在内含右奢赫工μ ^ ΰ 5 /士 有祕子的胺基酸。各成分添加量的 單位爲克(g)。 里的 處方(1) Ding with the above-mentioned hair dye cream R added amino acid and contains the right extravagant μ ^ ΰ 5 / Shi with the secret amino acid. The unit of the amount of each component added is gram (g). Prescription
No· 43No· 43
No. 44 膏基B 硝酸銀 70. 〇2. 0No. 44 Cream base B Silver nitrate 70. 〇 2. 0
胺基酸賴胺酸3.Amino acid lysine 3.
DHA pH 0· 3. 70. 0 3· 0 賴胺酸鹽酸鹽 賴胺酸鹽酸鹽 3· 0 4. 〇 0. 26 3. 1 6·2 用純化水製成l〇〇g。 上述處方N 〇 · 4 3的製劑最初的顏色爲白色,隨著時間 的推移變成茶色。該製劑的染色試驗結果為:髮束的顏色 爲稍f紅色的深茶色。 上述處方No. 44的製劑的染色試驗結果··帶有紅色的 較暗的淡黃色。 上述處方No. 45的製劑的染色試驗結果為··較暗的淡 29 200803906 • 黃色。 . 由上述處方Νο. 44製劑和Νο. 45製劑可知,賴胺酸鹽 酸鹽的氯離子會降低染髮力。 [實施例18] 實施例1 8中,使用下述染髮料膏基C。 [染髮料膏基C] 環狀矽酮 l.Og 曱基苯基石夕酮 1. 5 g • 西蒙得木油 1. Og 十六烧醇 5. 0 g 親油性硬脂酸單甘油醋 0. 4 g POE (5, 5)十六烷基醚 0· 6g ΡΌΕ (20)二十二烧基醚 0.6g 羊毛脂衍生物季銨鹽(50%溶液)_1. 2g 用純化水製成7 0 g。 該染髮料膏基C是黏度進一步高於上述染髮料膏基B 的乳白色的膏狀物。 實施例18所示範的製劑中,使用上述染髮料膏基C, 添加确酸銀、驗性胺基酸。各成分添加量的單位爲克(g )。 處方 No. 46 No. 47 No. 48 膏基C 70. 0 70. 0 70. 0 硝酸銀 1. 0 1. 0 1. 0 驗性胺基酸 賴胺酸2. 0 賴胺酸3. 0 賴胺酸1. 0 30 200803906 精胺酸i. ο ~~— 7·6 — 4· 7 用純化水製成100g。 上述處方No· 46的製劑最初的顏色爲白色,隨著時間 的推移變成灰黃色。該製劑的染色試驗結杲為··髮束的顏 色爲灰色。 上述處方No· 47的製劑最初的顏色爲白色,隨著時間 的推移不變色。該製劑的染色試驗結果為:髮束的顏色爲 余褐色。 上述處方No· 48的製劑最初的顏色爲白色,隨著時間 的推移變成灰黃色。該製劑的染色試驗結果為:髮束的顏 色爲茶褐色。 産業上的可利用性 本餐明涉及一種利用光能的單劑型染髮料,其通過調 即PH能夠使基於含銀鹽類的色調具有一定的範圍,並且 ^ 4劑是穩定的。此外,由於本發明的利用光能的染髮料 為單d型’所以無需像以往的染髮料那樣在使用之前需將 兩種液體進行混合,因此使用時操作簡單。 進步地來說’藉由在製劑中添加DHA可以使色調變 深。 ^再者,染髮料塗布於毛髮後,僅通過日光直射30分鐘 从上,銀或氧化銀即可牢固地附著於毛髮i,不會產生由 於鹽類或氧化反應等而導致毛髮的損傷或其他皮膚炎等。 31 200803906 而且,即使與永久染髮劑相比,也具 持時間齡具,9Η 〇 f 度的 了间早又長(2個月〜3個月)的效果。 由於具有這些作用/效果,本發 SA ^ 的利用光能的 木4料對於高齡化社會罝右拉 曰/、有極大的可利用性。 【圖式簡單說明】 益 【主要元件符號說明】DHA pH 0· 3. 70. 0 3· 0 lysine hydrochloride lysine hydrochloride 3· 0 4. 〇 0. 26 3. 1 6·2 Made of purified water to make l〇〇g. The formulation of the above prescription N 〇 · 4 3 is initially white in color and becomes brown over time. The result of the dyeing test of the preparation was that the color of the hair bundle was a dark brown with a slight f red color. The result of the dyeing test of the preparation of the above-mentioned prescription No. 44 was accompanied by a dark yellowish yellow color. The dyeing test result of the formulation of the above prescription No. 45 was darker than the light 29 200803906 • Yellow. It can be seen from the above prescription Νο. 44 preparation and Νο. 45 preparation that the chloride ion of the lysine salt reduces the hair dyeing power. [Example 18] In Example 18, the following hair dye base C was used. [Staining hair cream base C] Cyclohexanone l.Og decyl phenyl linoleine 1. 5 g • Simon's wood oil 1. Og hexadecanol 5. 0 g lipophilic stearic acid monoglycerin 0. 4 g POE (5, 5) cetyl ether 0·6g ΡΌΕ (20) docrosanyl ether 0.6g lanolin derivative quaternary ammonium salt (50% solution) _1. 2g made with purified water 7 0 g. The hair dye base C is a milky white paste having a viscosity higher than that of the above-mentioned hair dye base B. In the preparation exemplified in Example 18, the above-mentioned hair dye base C was used, and silver acetate and an acid-based acid were added. The unit of the amount of each component added is gram (g). Prescription No. 46 No. 47 No. 48 Cream base C 70. 0 70. 0 70. 0 Silver nitrate 1. 0 1. 0 1. 0 Amine amino acid lysine 2. 0 lysine 3. 0 赖Amino acid 1. 0 30 200803906 arginine i. ο ~~— 7·6 — 4· 7 100 g of purified water. The formulation of the above-mentioned prescription No. 46 was originally white in color and turned grayish yellow over time. The staining test of the preparation was that the color of the hair bundle was gray. The formulation of the above-mentioned prescription No. 47 was originally white in color and did not change color with time. The dyeing test result of the preparation was that the color of the hair bundle was brown. The formulation of the above-mentioned prescription No. 48 was initially white in color and turned grayish yellow over time. The result of the dyeing test of the preparation was that the color of the hair bundle was brownish brown. Industrial Applicability The present invention relates to a single-dose hair dye which utilizes light energy, which can have a certain range of color tone based on silver-containing salts by adjusting PH, and is stable. Further, since the hair dye using the light energy of the present invention is a single d-type, it is not necessary to mix the two liquids before use as in the conventional hair dye, and thus the operation is simple. Progressively, the color tone can be made deeper by adding DHA to the formulation. ^ Furthermore, after the hair dye is applied to the hair, it can be firmly adhered to the hair i by silver or silver oxide only by direct sunlight for 30 minutes, and there is no damage to the hair due to salt or oxidation reaction or the like. Dermatitis and so on. 31 200803906 Moreover, even when compared with permanent hair dyes, it has the effect of age and age, and the length of 9Η 〇 f is long and long (2 months to 3 months). Because of these effects/effects, the wood material using the light energy of the present SA ^ has great availability for the aging society. [Simple description of the diagram] Benefits [Main component symbol description]
顏色保 單劑型 益 # %>\Color policy dosage form Benefit # %>\
3232
Claims (1)
Applications Claiming Priority (1)
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JP2006074421A JP4184385B2 (en) | 2006-03-17 | 2006-03-17 | One-component hair dye using light energy |
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TW200803906A true TW200803906A (en) | 2008-01-16 |
Family
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TW096109095A TW200803906A (en) | 2006-03-17 | 2007-03-16 | One-part type hair dye utilizing optical energy |
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JP (1) | JP4184385B2 (en) |
KR (1) | KR20070094467A (en) |
CN (1) | CN101036623A (en) |
TW (1) | TW200803906A (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4349473B1 (en) * | 2008-12-26 | 2009-10-21 | コスメテックスローランド株式会社 | Hair dye |
US8974548B2 (en) | 2011-09-26 | 2015-03-10 | Conopco, Inc. | Hair composition |
JP5486106B1 (en) * | 2013-04-19 | 2014-05-07 | 川田 力也 | Photosensitive hair dye composition using water-soluble complex consisting of silver oxide and amino acid, and photosensitive hair dye |
MX358244B (en) * | 2013-05-09 | 2018-08-10 | Procter & Gamble | Hair care conditioning composition comprising histidine. |
JP6164543B1 (en) * | 2016-02-17 | 2017-07-19 | 株式会社アウラ | Photosensitive hair dye |
TWI641389B (en) * | 2016-06-15 | 2018-11-21 | 萬能學校財團法人萬能科技大學 | A hair care composition |
CN111484421A (en) * | 2020-04-29 | 2020-08-04 | 洛阳冠银生物科技有限公司 | Antibacterial silver ion compound, non-irritant silver ion antibacterial agent and preparation method and application thereof |
-
2006
- 2006-03-17 JP JP2006074421A patent/JP4184385B2/en not_active Expired - Fee Related
-
2007
- 2007-02-27 KR KR1020070019520A patent/KR20070094467A/en not_active Application Discontinuation
- 2007-03-16 CN CNA2007100883584A patent/CN101036623A/en active Pending
- 2007-03-16 TW TW096109095A patent/TW200803906A/en unknown
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JP2007246467A (en) | 2007-09-27 |
JP4184385B2 (en) | 2008-11-19 |
KR20070094467A (en) | 2007-09-20 |
CN101036623A (en) | 2007-09-19 |
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