TWI771134B - Natural hair dye and its commercialized formula - Google Patents
Natural hair dye and its commercialized formula Download PDFInfo
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Abstract
Description
本發明有關於染髮劑，特別是指基於天然成分的染髮劑組成及其商品化染髮劑配方。 The present invention pertains to hair dyes, in particular to hair dye compositions based on natural ingredients and to commercial hair dye formulations.
永久性染髮劑通常分為兩部分：第一部分為染料前體(中間體和偶合劑)加鹼液(通常為氨水，本發明以乙醇胺替代)；第二部分為氧化劑雙氧水。 Permanent hair dyes are usually divided into two parts: the first part is dye precursor (intermediate and coupling agent) plus lye (usually ammonia water, which is replaced by ethanolamine in the present invention); the second part is oxidant hydrogen peroxide.
前述永久性染髮劑的運作原理是先讓染料前體利用已被鹼液打開的毛鱗片滲透進入皮質中，再用雙氧水的強氧化性啟動化學反應，使中間體(primary intermediates)氧化與偶合劑偶合在頭髮中形成大分子量的分子，確保其不會被洗髮精洗掉。 The working principle of the aforementioned permanent hair dye is to first allow the dye precursor to penetrate into the cortex using the cuticles that have been opened by the lye, and then use the strong oxidative properties of hydrogen peroxide to initiate a chemical reaction to oxidize the intermediates (primary intermediates) and couplers. Coupling into the hair to form large molecular weight molecules, ensuring that they cannot be washed out by the shampoo.
目前市售染髮劑多數是以過氧化氫為調解劑以及氧化劑，氧化對苯二胺(PPD)、4-氨基苯酚(PAP)或是苯的芳香族化合類造成不同顏色的產生，再利用氨水成為鹼性的環境使偏酸性的頭髮能夠把毛鱗片打開而進行染色，而此過程所利用到的成份皆會對消費者的身體造成無法抹滅的傷害，特別在 PPD、PAP或是苯的芳香族化合類容易造成致癌性、過敏性等問題。 At present, most of the commercially available hair dyes use hydrogen peroxide as a regulator and oxidant, and oxidize p-phenylenediamine (PPD), 4-aminophenol (PAP) or aromatic compounds of benzene to produce different colors, and then use ammonia water. The alkaline environment enables acidic hair to open the cuticles for dyeing, and the ingredients used in this process will cause irreversible damage to the body of consumers, especially in Aromatic compounds such as PPD, PAP or benzene are prone to cause carcinogenicity, allergy and other problems.
為了克服前述非天然染髮劑的使用問題，另發展出一種天然的植物染，常見於植物染的染料有指甲花、蓼藍、咖啡或茶，但是使用純粹的天然植物染料來染髮其實是不能持久的，染料只會附著在毛鱗片外面，經不起多次的洗髮，最多兩三周就會褪色。是以，若一般市售的「植物染」染髮產品的效果可以撐幾個月，代表這些染髮產品還是添加了氨水、過氧化氫此等具有刺激性以及破壞性物質，才能撐開毛鱗片並把原來髮色漂白達到染色持久之效果。 In order to overcome the problem of the use of the aforementioned non-natural hair dyes, a natural plant dye has been developed. The dyes commonly used in plant dyes include henna, polygonum indigo, coffee or tea, but the use of pure natural plant dyes to dye hair is not durable. Yes, the dye will only stick to the outside of the cuticles and will not stand up to multiple shampooing and will fade in two or three weeks at most. Therefore, if the effect of the "plant dyeing" hair dyeing products on the market can last for several months, it means that these hair dyeing products are still added with irritating and destructive substances such as ammonia water and hydrogen peroxide, in order to stretch the scales and prevent the hair. Bleaching the original hair color to achieve the effect of long-lasting dyeing.
然而，目前已知的天然染劑均面臨到相同的問題，即染色時間長、耐皂洗能力弱、顏色飽和度低且多樣性不比合成染劑；此外，在染色效果的部分，市售標榜天然染劑為了促進染色效果需要再額外添加別種化學物質，使得染劑的刺激性增加；且市售天然染劑受限於原料的關係導致其顏色的多樣性不佳，不如以化學物質調製的染劑擁有較多元的顏色。 However, the currently known natural dyes all face the same problems, namely long dyeing time, weak soaping resistance, low color saturation and no diversity compared to synthetic dyes; in addition, in the part of dyeing effect, commercially available advertised In order to promote the dyeing effect, natural dyes need to add other chemical substances, which increases the irritation of the dyes; and the commercially available natural dyes are limited by the relationship between raw materials, resulting in poor color diversity, so it is better to use chemical substances. Dye has more colors.
另值得注意的是，目前已經研究出以漆酶催化植物酚酸聚合產物實現有效染髮的天然染髮劑，但該天然染髮劑仍存在染髮時間過長、不耐水洗、不耐照光以及染後髮質脆弱等問題，為了克服上述之問題，需要找出能夠縮短染色時間並提升毛髮的染色以及耐水洗效果與耐照光效果，並改善毛髮的機械性質。 It is also worth noting that a natural hair dye that uses laccase-catalyzed plant phenolic acid polymerization products to achieve effective hair dyeing has been researched, but the natural hair dye still has the problems of long hair dyeing time, insufficiency to washing, light resistance, and hair dyeing after dyeing. In order to overcome the above-mentioned problems, it is necessary to find ways to shorten the dyeing time, improve the dyeing effect of the hair, the effect of washing resistance and light resistance, and improve the mechanical properties of the hair.
為克服上述技術問題，本發明之目的在於提供一種天然染髮劑及其商品化配方，該天然染髮劑包括植物酚酸染劑(漆酶、阿魏酸)、金屬媒染劑(氯化鈣)以及界面活性劑，且該天然染髮劑經加入高分子增稠劑、抗氧化劑 等添加劑以形成商品化配方。藉此，透過以天然植物酚酸作為主要原料以達到減低化學成分對人體造成的傷害以及刺激性之目的；透過添加界面活性劑達到提升染色、耐水洗以及提高染色後毛髮拉伸力的效果；透過添加高分子增稠劑使商品化染髮劑的黏度與染色效果獲得提升；透過添加維生素C使染色後毛髮具有更好的UV光照耐受性。是以，本發明透過提供的天然染髮劑及其商品化配方，實現具有實用性以及商品化的功能的染髮劑。 In order to overcome the above-mentioned technical problems, the object of the present invention is to provide a kind of natural hair dye and commercialized formula thereof, and this natural hair dye comprises plant phenolic acid dye (laccase, ferulic acid), metal mordant (calcium chloride) and Surfactant, and the natural hair dye is added with polymer thickener, antioxidant and other additives to form commercial formulations. In this way, by using natural plant phenolic acid as the main raw material, the purpose of reducing the damage and irritation caused by chemical components to the human body is achieved; by adding surfactants, the effects of improving dyeing, washing resistance and improving hair stretching force after dyeing are achieved; The viscosity and dyeing effect of commercial hair dyes are improved by adding polymer thickeners; the dyed hair has better UV light resistance by adding vitamin C. Therefore, the present invention realizes the hair dye with practical and commercial functions through the provided natural hair dye and its commercial formulation.
緣是，為達上述目的，本發明所提供一種天然染髮劑，其包括：漆酶催化植物酚酸染劑，包括植物酚酸染劑及金屬媒染劑，其中，該植物酚酸染劑包含阿魏酸、漆酶及溶劑，該阿魏酸於該植物酚酸染劑中的濃度為20mM，該漆酶的於該植物酚酸染劑中的添加量為每100mL溶劑中添加0.1g漆酶，該溶劑是濃度為50wt%的乙醇水溶液；該金屬媒染劑為氯化鈣；界面活性劑，選自十六烷基三甲基溴化銨(CTAB)、十六烷基三甲基氯化銨(CTAC)、十二烷基硫酸鈉(SDS/SLS)、十二烷基苯磺酸鈉(SDBS)、椰子油醯丙基甜菜鹼(CAPB)、TWEEN20及TWEEN80的其中一種；該界面活性劑以臨界微胞濃度的1至5倍添加於該漆酶催化植物酚酸染劑中。 The reason is that, in order to achieve the above purpose, the present invention provides a natural hair dye, which comprises: a laccase-catalyzed plant phenolic acid dye, including a plant phenolic acid dye and a metal mordant, wherein the plant phenolic acid dye comprises a Folic acid, laccase and solvent, the concentration of the ferulic acid in the plant phenolic acid dye is 20mM, and the addition amount of the laccase in the plant phenolic acid dye is 0.1g of laccase per 100mL of solvent , the solvent is an ethanol aqueous solution with a concentration of 50wt%; the metal mordant is calcium chloride; the surfactant is selected from cetyl trimethyl ammonium bromide (CTAB), cetyl trimethyl chloride One of Ammonium (CTAC), Sodium Dodecyl Sulfate (SDS/SLS), Sodium Dodecyl Benzene Sulfonate (SDBS), Coco Propyl Betaine (CAPB), TWEEN20 and TWEEN80; the interface activity The laccase catalyzed plant phenolic acid dye is added at 1 to 5 times the critical micelle concentration.
其中，本發明天然染髮劑的界面活性劑較佳選自5mM的十六烷基三甲基溴化銨(CTAB)、5.5mM的十六烷基三甲基氯化銨(CTAC)、15mM的十二烷基硫酸鈉(SDS/SLS)、2.5mM的十二烷基苯磺酸鈉(SDBS)、0.075mM的TWEEN80或者6mM的椰子油醯丙基甜菜鹼(CAPB)。 Wherein, the surfactant of the natural hair dye of the present invention is preferably selected from 5 mM cetyl trimethyl ammonium bromide (CTAB), 5.5 mM cetyl trimethyl ammonium chloride (CTAC), 15 mM cetyl trimethyl ammonium chloride (CTAC) Sodium dodecyl sulfate (SDS/SLS), 2.5 mM sodium dodecylbenzene sulfonate (SDBS), 0.075 mM TWEEN80, or 6 mM cocopropyl betaine (CAPB).
其中，本發明天然染髮劑還包括選自***膠(Gum Arabic)、明膠(Gelatin)、羥乙基纖維素(HEC)或其中二種以上材料的組成的高分子增稠劑。 Wherein, the natural hair dye of the present invention also includes a polymer thickener selected from Gum Arabic (Gum Arabic), gelatin (Gelatin), hydroxyethyl cellulose (HEC) or two or more of them.
其中，本發明天然染髮劑還包括作為抗氧化劑使用的維生素C。 Among them, the natural hair dye of the present invention also includes vitamin C used as an antioxidant.
本發明另提供一種天然染髮劑的商品化配方，包括：漆酶催化植物酚酸染劑，包括植物酚酸染劑及金屬媒染劑；其中，該植物酚酸染劑包含阿魏酸、漆酶及溶劑，該阿魏酸於該植物酚酸染劑中的濃度為20mM，該漆酶的於該植物酚酸染劑中的添加量為每100mL溶劑中添加0.1g漆酶，該溶劑是濃度為50wt%的乙醇水溶液；該金屬媒染劑為氯化鈣；界面活性劑，選自十六烷基三甲基溴化銨(CTAB)或十六烷基三甲基氯化銨(CTAC)；高分子增稠劑，包括明膠及***膠；抗氧化劑，為維生素C；其中，以該配方的總重量計，包括90.97至95.26wt%的植物酚酸染劑，0.92至0.96wt%的金屬媒染劑，0.18至0.36wt%的界面活性劑，1至2.5wt%的明膠，2.5至5wt%的***膠，以及0.1至0.25wt%的維生素C。 The present invention further provides a commercial formulation of a natural hair dye, comprising: a laccase-catalyzed plant phenolic acid dye, including a plant phenolic acid dye and a metal mordant; wherein, the plant phenolic acid dye comprises ferulic acid, laccase and solvent, the concentration of the ferulic acid in the plant phenolic acid dye is 20mM, the addition amount of the laccase in the plant phenolic acid dye is 0.1g of laccase per 100mL of solvent, and the solvent is the concentration is a 50wt% ethanol aqueous solution; the metal mordant is calcium chloride; the surfactant is selected from cetyltrimethylammonium bromide (CTAB) or cetyltrimethylammonium chloride (CTAC); Macromolecular thickeners, including gelatin and gum arabic; antioxidants, vitamin C; wherein, based on the total weight of the formulation, including 90.97 to 95.26wt% of plant phenolic acid dyes, 0.92 to 0.96wt% of metal mordant dyes agent, 0.18 to 0.36 wt% surfactant, 1 to 2.5 wt% gelatin, 2.5 to 5 wt% gum arabic, and 0.1 to 0.25 wt% vitamin C.
其中，經本發明天然染髮劑的商品化配方染色後的毛髮未水洗的色差值(DE*)為57.29至63.2；該配方染色後的毛髮經1至10次水洗後的色差值(DE*)為41.08至62.34。 Wherein, the color difference value (DE*) of the unwashed hair dyed by the commercial formulation of the natural hair dye of the present invention is 57.29 to 63.2; the color difference value (DE*) of the hair dyed by the formula after 1 to 10 washings ) from 41.08 to 62.34.
其中，經本發明天然染髮劑的商品化配方染色後的毛髮未經水洗的著色力(K/S)為21.39至25.75；該配方染色後的毛髮經1至10次水洗後的著色力(K/S)為10.95至22.23。 Wherein, the tinting strength (K/S) of the hair dyed by the commercial formulation of the natural hair dye of the present invention without washing is 21.39 to 25.75; S) was 10.95 to 22.23.
其中，經本發明天然染髮劑的商品化配方染色後的毛髮未經水洗的色相角(h°)為49.41至55.28；該配方染色後的毛髮經1至10次水洗後的色相角(h°)為51.15至77.87。 Wherein, the hue angle (h°) of the hair dyed by the commercial formulation of the natural hair dye of the present invention without washing is 49.41 to 55.28; the hue angle (h°) of the hair dyed by the formula after 1 to 10 washings was 51.15 to 77.87.
其中，經本發明天然染髮劑的商品化配方染色後的毛髮未經UV光照的色差值(DE*)為59.71至63.2，著色力(K/S)為25.35至26.47，色相角(h°)為43.32至45.5；該配方染色後的毛髮經光照1至30日後的色差值(DE*)為50.14至62.55，著色力(K/S)為21.15至25.91，色相角(h°)為44.55至58.62。 Wherein, the color difference value (DE*) of the hair dyed by the commercial formulation of the natural hair dye of the present invention without UV light is 59.71 to 63.2, the tinting strength (K/S) is 25.35 to 26.47, and the hue angle (h°) 43.32 to 45.5; the color difference value (DE*) of the hair dyed by the formula after exposure to light for 1 to 30 days is 50.14 to 62.55, the tinting strength (K/S) is 21.15 to 25.91, and the hue angle (h°) is 44.55 to 58.62.
其中，經本發明天然染髮劑的商品化配方染色後的毛髮斷裂強度(MPa)為150.09至171.57MPa。 Wherein, the hair breaking strength (MPa) after dyeing with the commercial formulation of the natural hair dye of the present invention is 150.09 to 171.57 MPa.
有關於本發明為達成上述目的，所採用之技術、手段及其他功效，茲舉較佳可行實施例並配合圖式詳細說明如後。 Regarding the techniques, means and other effects adopted by the present invention to achieve the above-mentioned objects, preferred feasible embodiments are given and described in detail in conjunction with the drawings as follows.
為利於對本發明的瞭解，以下結合實施例進行說明。 In order to facilitate the understanding of the present invention, the following description is made with reference to the embodiments.
本發明提供天然染髮劑及其商品化配方。其中，該天然染髮劑主要包括植物酚酸染劑及金屬媒染劑及；該植物酚酸染劑是在乙醇水溶液中以漆酶對阿魏酸(植物酚酸)進行催化反應製得；該金屬媒染劑是氯化鈣。進一步地，該天然染髮劑透過加入包括界面活性劑、高分子增稠劑、抗氧化劑等添加物形成商品化配方，以達到提供具有實用性及商品化功能的染髮劑。 The present invention provides natural hair dyes and commercial formulations thereof. Wherein, the natural hair dye mainly includes plant phenolic acid dye and metal mordant; the plant phenolic acid dye is prepared by catalyzing reaction of ferulic acid (plant phenolic acid) with laccase in ethanol aqueous solution; The mordant is calcium chloride. Further, the natural hair dye is formed into a commercial formulation by adding additives including surfactants, polymer thickeners, antioxidants, etc., so as to provide a hair dye with practical and commercial functions.
具體地，本發明天然染髮劑的商品化配方，以該配方的總重量計，包括90.97至95.26wt%的植物酚酸染劑(20mM的阿魏酸酚酸)，0.92至0.96wt%的金屬媒染劑(氯化鈣)，0.18至0.36wt%的界面活性劑，3.5至7.5wt%的高分子增稠劑，以及0.1至0.25wt%的抗氧化劑。 Specifically, the commercial formulation of the natural hair dye of the present invention, based on the total weight of the formulation, comprises 90.97 to 95.26 wt % of a plant phenolic acid dye (20 mM ferulic acid phenolic acid), 0.92 to 0.96 wt % of a metal Mordant (calcium chloride), 0.18 to 0.36 wt % of surfactant, 3.5 to 7.5 wt % of polymeric thickener, and 0.1 to 0.25 wt % of antioxidant.
於本發明實施例中，該漆酶催化植物酚酸染劑包括植物酚酸染劑及金屬媒染劑；該植物酚酸染劑包含阿魏酸、漆酶及溶劑，該阿魏酸於該植物酚酸染劑中的濃度為20mM，該漆酶的於該植物酚酸染劑中的添加量為每100mL 溶劑中添加0.1g漆酶，該溶劑是濃度為50wt%的乙醇水溶液；該金屬媒染劑為氯化鈣。 In the embodiment of the present invention, the laccase-catalyzed plant phenolic acid dye includes a plant phenolic acid dye and a metal mordant; the plant phenolic acid dye includes ferulic acid, laccase and a solvent, and the ferulic acid is present in the plant. The concentration in the phenolic acid dye is 20mM, and the addition amount of the laccase in the plant phenolic acid dye is per 100mL 0.1 g of laccase is added to the solvent, which is an aqueous ethanol solution with a concentration of 50 wt %; the metal mordant is calcium chloride.
該界面活性劑選自十六烷基三甲基溴化銨(CTAB)、十六烷基三甲基氯化銨(CTAC)、十二烷基硫酸鈉(SDS/SLS)、十二烷基苯磺酸鈉(SDBS)、椰子油醯丙基甜菜鹼(CAPB)、TWEEN20及TWEEN80的其中一種。較佳地，該界面活性劑以臨界微胞濃度的1至5倍添加於該漆酶催化植物酚酸染劑中。 The surfactant is selected from cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), sodium dodecyl sulfate (SDS/SLS), dodecyl One of sodium benzene sulfonate (SDBS), coconut oil propyl betaine (CAPB), TWEEN20 and TWEEN80. Preferably, the surfactant is added to the laccase-catalyzed plant phenolic acid dye at 1 to 5 times the critical micelle concentration.
本發明使用導電度法測量不同濃度的界面活性劑的導電度，當界面活性劑的濃度接近臨界微胞濃度時，導電度會出現明顯的上升，後趨於平緩，表示溶液達到了臨界微胞濃度，從而獲得如下表1的界面活性劑的臨界微胞濃度。 The present invention uses the conductivity method to measure the conductivity of different concentrations of surfactants. When the concentration of the surfactant is close to the critical micelle concentration, the conductivity will increase significantly, and then tend to be flat, indicating that the solution reaches the critical micelle concentration. concentration to obtain the critical micelle concentration of the surfactant in Table 1 below.
該高分子增稠劑選自***膠(Gum Arabic)、明膠(Gelatin)、羥乙基纖維素(HEC)或其中二種以上材料的組成。較佳為明膠與***膠之組合。 The polymer thickener is selected from Gum Arabic, Gelatin, hydroxyethyl cellulose (HEC) or a combination of two or more of them. A combination of gelatin and acacia is preferred.
該抗氧化劑可選自維生素C(ascorbic acid)、維生素E(α-tocopherol)或榖胱甘肽(glutathione，GSH)。於本發明實施例中，較佳以維生素C作為抗氧化 劑。 The antioxidant may be selected from vitamin C (ascorbic acid), vitamin E (α-tocopherol) or glutathione (GSH). In the embodiment of the present invention, vitamin C is preferably used as antioxidant agent.
其中，如下式(1)，***膠交聯機制是透過漆酶氧化***膠主要結構中的***醣側鏈上的阿魏酸進行交聯。酯化到***醣側鏈的阿魏酸，是利用氧化還原酶(如漆酶)，因此漆酶涉及***膠交聯反應與阿魏酸催化反應，故***膠能當作為染髮劑增稠使用。 Wherein, as shown in the following formula (1), the cross-linking mechanism of gum arabic is through laccase oxidation of ferulic acid on the arabinose side chain in the main structure of gum arabic for cross-linking. Ferulic acid esterified to arabinose side chain uses oxidoreductase (such as laccase), so laccase is involved in the cross-linking reaction of gum arabic and the catalyzed reaction of ferulic acid, so gum arabic can be used as a hair dye to thicken .
其中，如下式(2)，顯示十六烷基三甲基溴化銨(CTAB)結構式，CTAB為陽離子型界面活性劑帶有正電荷，而頭髮帶負電，因此可以藉由陽離子型界面活性劑使染髮劑更容易吸附在頭髮，呈現更好的染色效果且能夠縮短染髮時間。 Among them, the following formula (2) shows the structural formula of cetyltrimethylammonium bromide (CTAB), CTAB is a cationic surfactant with a positive charge, and the hair is negatively charged, so it can be activated by a cationic surfactant The agent makes it easier for the hair dye to adsorb on the hair, showing better dyeing results and shortening the hair dyeing time.
式(2)：
其中，如下式(3)，顯示十六烷基三甲基氯化銨(CTAC)結構式，CTAC為陽離子型界面活性劑帶有正電荷，而頭髮帶負電，因此可以藉由陽離子型界面活性劑使染髮劑更容易吸附在頭髮，呈現更好的染色效果且能夠縮短染髮時間。 Among them, the following formula (3) shows the structural formula of cetyltrimethylammonium chloride (CTAC), CTAC is a cationic surfactant with a positive charge, and the hair is negatively charged, so it can be activated by a cationic surfactant The agent makes it easier for the hair dye to adsorb on the hair, showing better dyeing results and shortening the hair dyeing time.
其中，如下式(4)，顯示維生素C抗氧化機制圖，維生素C可以直接與羥基自由基(hydroxyl radicals)作用，產生不活躍的自由基產物，接著被代謝成草酸排出人體，添加到染髮劑是對提升頭髮的耐照光性是有幫助的。 Among them, the following formula (4) shows the diagram of the antioxidant mechanism of vitamin C. Vitamin C can directly interact with hydroxyl radicals to produce inactive free radical products, which are then metabolized into oxalic acid and excreted from the human body, and added to hair dyes It is helpful for improving the light resistance of hair.
其中，如下式(5)，顯示明膠化學結構式，明膠可透過漆酶與阿魏酸產生交聯反應，使染髮劑增稠。 Among them, the following formula (5) shows the chemical structural formula of gelatin, and gelatin can generate a cross-linking reaction with ferulic acid through laccase to thicken the hair dye.
式(5)：
其中，如下式(6)，顯示漆酶催化反應機制，漆酶是從反應底物中抓取單電子讓化合物變成能反應的自由基，該自由基形成中間體，透過偶合反應以生成二聚、低聚、聚合或交叉偶合產物。 Among them, the following formula (6) shows the catalytic reaction mechanism of laccase. Laccase captures a single electron from the reaction substrate to turn the compound into a reactive free radical. The free radical forms an intermediate and generates dimerization through a coupling reaction. , oligomeric, polymeric or cross-coupling products.
以上說明了本發明天然染髮劑及其商品化配方的組成配比。以下說明本發明天然染髮劑及其商品化配方的製法及效能檢測實施例。 The above describes the composition ratio of the natural hair dye of the present invention and its commercial formulation. The following describes the preparation method and efficacy testing examples of the natural hair dye of the present invention and its commercial formulation.
需說明的是，於本發明實施例中，為避免染色頭髮的染色效果受原有髮色影響，本發明染髮劑使用時，較佳經過前處理程序後進行染色。具體地，所述前處理程序的方法步驟包括：漂髮步驟：提供漂粉及雙氧乳，將前述兩者混合後均勻塗敷於毛髮表面，以去除毛髮中的麥拉寧色素(melanin)達到漂白目的；毛鱗片打開步驟：提供鹼液，將漂髮後的毛髮塗敷鹼液，以使毛 髮表面的毛鱗片與鹼液反應呈現張開狀態。 It should be noted that, in the embodiment of the present invention, in order to prevent the dyeing effect of dyed hair from being affected by the original hair color, when the hair dye of the present invention is used, it is preferable to dye it after a pretreatment procedure. Specifically, the method steps of the pretreatment procedure include: a hair bleaching step: providing bleaching powder and hydrogen peroxide, mixing the aforementioned two and then evenly coating the hair surface to remove the melanin pigment in the hair (melanin) To achieve the purpose of bleaching; hair cuticle opening steps: provide lye, and apply lye to the bleached hair to make the hair The cuticles on the hair surface react with the lye to open up.
於本發明實施例中，該鹼液較佳為乙醇胺，以降低對人體皮膚的刺激。 In the embodiment of the present invention, the lye is preferably ethanolamine, so as to reduce the irritation to human skin.
此外，於本發明實施例中，烘乾後的染色毛髮係利用桌上型色差儀測量染色結果，本發明以CIE L*a*b*色度空間的相關參數值(如L*值、a*值、b*值)來描述製得之染髮劑所染出的毛髮顏色。所述CIE L*a*b*(CIELAB)是慣常用來描述人眼可見的所有顏色的最完備的色彩模型。該色彩模型是為這個特殊目的而由國際照明委員會(Commission Internationale de l'Eclairage的首字母是CIE)提出的。其中，L、a和b後面的星號(*)是全名的一部分，L*、a*和b*是用於描述此系統的重要參數，其係三個基本坐標表示顏色的亮度(L*，L*=0指生黑色而L*=100指示白色)，它在紅色/品紅色和綠色之間的位置(a*負值指示綠色而正值指示品紅)和它在黃色和藍色之間的位置(b*負值指示藍色而正值指示黃色)。 In addition, in the embodiment of the present invention, the dyed hair after drying is measured by a desktop colorimeter, and the present invention uses the relevant parameter values of the CIE L*a*b* chromaticity space (such as L* value, a * value, b* value) to describe the hair color dyed by the prepared hair dye. The CIE L*a*b* (CIELAB) is the most complete color model conventionally used to describe all colors visible to the human eye. The color model was proposed by the Commission Internationale de l'Eclairage (the initials are CIE) for this particular purpose. Among them, the asterisk (*) after L, a and b is part of the full name, and L*, a* and b* are important parameters used to describe this system, which are three basic coordinates representing the brightness of the color (L* , L*=0 for raw black and L*=100 for white), its position between red/magenta and green (a* negative values indicate green and positive values indicate magenta) and its position in yellow and blue (b* negative values indicate blue and positive values indicate yellow).
實施例1： Example 1 :
漆酶催化植物酚酸染劑的製法步驟包括：阿魏酸酚酸配製步驟：將粉末狀的阿魏酸溶於濃度為50wt%的乙醇水溶液，以配製濃度為20mM的阿魏酸酚酸溶液；漆酶添加步驟：以每100mL阿魏酸酚酸溶液添加0.1g漆酶的比例，將漆酶加入阿魏酸酚酸溶液中，並以超音波震盪1小時；pH值調整步驟：使用0.1M氫氧化鈉水溶液調整pH值至8，再以超音波震盪1小時，製得植物酚酸染劑；金屬媒染劑添加步驟：氯化鈣作為金屬媒染劑添加至該植物酚 酸染劑中，經調整pH值後完成顏色，製得漆酶催化植物酚酸染劑。 The preparation method of the laccase-catalyzed plant phenolic acid dye includes: the ferulic acid phenolic acid preparation step: the powdered ferulic acid is dissolved in an ethanol aqueous solution with a concentration of 50wt% to prepare a ferulic acid phenolic acid solution with a concentration of 20mM ; Laccase addition step: add 0.1 g of laccase per 100 mL of ferulic acid phenolic acid solution, add laccase to the ferulic acid phenolic acid solution, and shake with ultrasonic for 1 hour; pH adjustment step: use 0.1 The pH value of M sodium hydroxide aqueous solution was adjusted to 8, and then ultrasonically oscillated for 1 hour to obtain a plant phenolic acid dye; metal mordant addition step: calcium chloride was added as a metal mordant to the plant phenolic dye In the acid dye, the color is completed after adjusting the pH value, and the laccase catalyzed plant phenolic acid dye is prepared.
實施例2：Example 2:
從導電度計法得到界面活性劑的臨界微胞濃度(表1)後，本發明實施例2使用濃度為20mM的阿魏酸酚酸染劑製成漆酶催化植物酚酸染劑(以下簡稱漆酶染劑)，並於該漆酶染劑中添加界面活性劑以測試對染色效果的影響。由於界面活性劑經水洗後會被稀釋，故實施例2使用臨界微胞濃度為一、二、五、十倍的界面活性劑作為添加劑進行染色(表2)以及水洗(表3)測試，測試結果如下表2、表3所示。 After obtaining the critical micelle concentration (Table 1) of the surfactant from the conductivity meter method, Example 2 of the present invention uses the ferulic acid phenolic acid dye with a concentration of 20 mM to make the laccase-catalyzed plant phenolic acid dye (hereinafter referred to as the laccase dye), and adding surfactant to the laccase dye to test the effect on the dyeing effect. Since the surfactant will be diluted after washing with water, in Example 2, the surfactant with a critical micelle concentration of one, two, five, and ten times was used as an additive for dyeing (Table 2) and water washing (Table 3) tests. The results are shown in Tables 2 and 3 below.
從表2可知，界面活性劑添加於染髮劑對毛髮染色後，陽離子型界面活性劑(CTAB、CTAC)在染色效果的呈現比陰離子(SDS/SLS、SDBS)、非離子(TWEEN80、TWEEN20)以及兩性型界面活性劑(CAPB)更好。此外，陽離子界面活性劑添加後，透過色差計讀值結果可以發現頭髮的a*值有上升，表示頭髮顏色往紅靠近，並且色差值以及著色力也有所上升，表示陽離子界面活性劑的添加對於染髮劑是具有增效的作用，陰離子界面活性劑、兩性離子型與非離子型的TWEEN80皆具有增效的能力，從CMC濃度中可以看到，陽離子界面活性劑的CTAB、CTAC在5倍的CMC濃度下與十倍的的濃度在染色結果相近，表示CTAB、CTAC的濃度在5倍的添加時，染色效果即可達到穩定；陰離子界面活性劑的SDS/SLS、SDBS在到達兩倍的CMC濃度時，染色效果達到穩定。非離子型界面活性劑TWEEN20在5倍的CMC濃度時擁有較好的染色效果，而TWEEN80在不同CMC倍數濃度下的染色效果皆是相近。兩性型界面活性劑CAPB在兩倍CMC濃度下即可達到穩定的效果。以上各種界面活性劑形成穩定染色結果的較佳CMC倍數濃度經換算成莫耳體積濃度(mM)依序為：CTAB添加濃度較佳為5mM、 CTAC添加濃度較佳為5.5mM、SDS/SLS添加濃度較佳為15mM、SDBS添加濃度較佳為2.5mM、TWEEN80添加濃度較佳為0.075mM以及CAPB添加濃度較佳為6mM。 It can be seen from Table 2 that after the surfactant is added to the hair dye to dye the hair, the cationic surfactant (CTAB, CTAC) exhibits a higher dyeing effect than anionic (SDS/SLS, SDBS), non-ionic (TWEEN80, TWEEN20) and Amphoteric surfactants (CAPB) are better. In addition, after the cationic surfactant is added, it can be found that the a* value of the hair has increased through the color difference meter reading results, indicating that the hair color is closer to red, and the color difference value and coloring force have also increased, indicating the addition of cationic surfactant. It has a synergistic effect on hair dyes. Anionic surfactants, zwitterionic and non-ionic TWEEN80 all have synergistic abilities. It can be seen from the CMC concentration that CTAB and CTAC of cationic surfactants are 5 times higher than those of cationic surfactants. The staining results are similar at the CMC concentration of 10 times to that of 10 times, which means that when the concentration of CTAB and CTAC is added at 5 times, the staining effect can be stabilized; SDS/SLS and SDBS of anionic surfactants reach twice At the concentration of CMC, the dyeing effect was stable. The non-ionic surfactant TWEEN20 has a better dyeing effect at 5 times the CMC concentration, while the dyeing effect of TWEEN80 at different CMC multiple concentrations is similar. The amphoteric surfactant CAPB can achieve stable effect at twice the concentration of CMC. The preferred CMC multiple concentrations of the above various surfactants to form stable staining results are converted into molar volume concentrations (mM) in order: CTAB is preferably added at a concentration of 5 mM, Preferably, CTAC is added at a concentration of 5.5 mM, SDS/SLS is preferably added at a concentration of 15 mM, SDBS is preferably added at a concentration of 2.5 mM, TWEEN80 is preferably added at a concentration of 0.075 mM, and CAPB is preferably added at a concentration of 6 mM.
如上表3，顯示表3實施例經過一次水洗後的染色效果。其中，陽離子型界面活性劑添加的染髮劑對於頭髮顏色的保持最為良好，在5倍CMC濃度的a*值仍然具有25以上，頭髮顏色為橘黃色，而沒有添加的染髮劑經過一次水洗後a*值衰退至6.58，頭髮顏色變為黃色，表示添加了陽離子界面活性劑後，對於a*值的保持是有所幫助的，陰離子界面活性劑水洗後可以發現在2倍的CMC濃度下，SDS以及SDBS具有穩定的結果，TWEEN80經過水洗後可以發現在5倍的CMC濃度開始具有穩定的結果，椰子油醯丙基甜菜鹼從2倍的CMC濃度開始具有穩定的結果。 As shown in Table 3 above, the dyeing effect of the examples in Table 3 after one wash is shown. Among them, the hair dyes added with cationic surfactants have the best retention of hair color, and the a* value of 5 times the CMC concentration still has a value of more than 25, and the hair color is orange. The * value declined to 6.58, and the hair color changed to yellow, indicating that the addition of the cationic surfactant was helpful for the retention of the a* value. As well as SDBS has stable results, TWEEN80 can be found to have stable results starting at 5 times the CMC concentration after washing, and coconut oil propyl betaine has stable results starting from 2 times the CMC concentration.
實施例3：Example 3:
由實施例2的漆酶催化植物酚酸染劑添加界面活性劑染色效果可知，陽離子型界面活性劑(CTAB、CTAC)的添加能夠實現較佳的染色效果，故以濃度為5mM的CTAB與5.5mM的CTAC作為實施例3的固定添加物，並選擇10、30以及60分鐘作為染色時間進行比較，以測試添加界面活性劑對染髮時間的影響(表4)及其水洗後染色效果(表5)。 From the dyeing effect of the laccase-catalyzed plant phenolic acid dye added with surfactant in Example 2, it can be seen that the addition of cationic surfactant (CTAB, CTAC) can achieve better dyeing effect, so CTAB with a concentration of 5mM and 5.5 mM CTAC was used as the fixed additive in Example 3, and 10, 30 and 60 minutes were selected as the dyeing time for comparison, to test the effect of adding surfactant on the dyeing time (Table 4) and the dyeing effect after washing (Table 5). ).
由表4可知，添加界面活性劑的染髮劑的色差值及著色力在染髮後30分鐘時即可達到穩定，與染髮60分鐘的結果相近，且比未添加的酚酸染劑(阿魏酸酚酸濃度為20mM與氯化鈣製成的漆酶催化植物酚酸染劑，縮寫FA+Ca)在色差值以及著色力皆保持良好。 As can be seen from Table 4, the color difference value and tinting strength of the hair dye added with surfactant can reach stability after 30 minutes of dyeing, which is similar to the result of dyeing hair 60 minutes, and compared with the phenolic acid dye (ferulic acid) that is not added. The laccase-catalyzed plant phenolic acid dye made of acid phenolic acid concentration of 20mM and calcium chloride (abbreviated as FA+Ca) maintained good color difference value and tinting strength.
接著使用0.1M十二烷基硫酸鈉溶液作為洗劑以磁石攪拌器調整轉速為100rpm水洗染過色的毛髮10分鐘，測試經過一次水洗後色差值以及著色的保持狀況，如下表5。經過一次水洗後發現，沒有添加界面活性劑的酚酸染劑(FA+Ca)的色差值以及著色力在第60分鐘後才能達到較為良好的效果，而添加了陽離子界面活性劑後在第30分鐘時就達到較為穩定的效果，與60分鐘的結果比較為相近，表示添加了陽離子界面活性劑對於縮短染色時間是有幫助的，可以將染色時間縮短為30分鐘，同時對於色差值以及著色力是有上升的。 Then use 0.1M sodium lauryl sulfate solution as lotion with magnet stirrer to adjust the rotating speed to wash the dyed hair for 10 minutes at 100rpm, and test the color difference value and color retention status after one wash, as shown in Table 5 below. After one wash, it was found that the color difference value and coloring strength of the phenolic acid dye (FA+Ca) without the addition of the surfactant could achieve a relatively good effect after the 60th minute, while the cationic surfactant was added in the first A relatively stable effect was achieved at 30 minutes, which was similar to the result at 60 minutes, indicating that the addition of cationic surfactants was helpful for shortening the dyeing time, and the dyeing time could be shortened to 30 minutes. There is an increase in tinting strength.
實施例4：Example 4:
實施例4是在漆酶催化植物酚酸染劑為20mM阿魏酸酚酸染劑添加氯化鈣，分別添加陽離子型界面活性劑5mM CTAB以及5.5mM CTAC的固定組成上，進一步分別添加選自明膠(縮寫GE)、***膠(縮寫GA)或羥乙基纖維素(縮寫HEC)且添加量分別為1wt%、2.5wt%、5wt%的高分子增稠劑，以測試添加高分子增稠劑後的染劑染色效果以及水洗效果，如下列表6至表8所示。 In Example 4, the laccase catalyzed plant phenolic acid dye was 20 mM ferulic acid phenolic acid dye added with calcium chloride, and the cationic surfactant 5 mM CTAB and 5.5 mM CTAC were respectively added to the fixed composition, and were further added respectively. Gelatin (abbreviated as GE), gum arabic (abbreviated as GA) or hydroxyethyl cellulose (abbreviated as HEC) and added in an amount of 1wt%, 2.5wt%, and 5wt%, respectively, to test the addition of polymer thickening agents The dyeing effect and washing effect of the dye after the agent are shown in Tables 6 to 8 below.
如下表6，明膠添加的量在1wt%及2.5wt%時，毛髮染色的色差值以及著色力相近，但是添加量在5wt%時，添加量過多導致染劑產生凝結，凝結成塊狀後染色效果下降。經過一次水洗後，1wt%及2.5wt%的添加色差值與著色力無明顯下降，但是5wt%的明膠經過一次水洗後，顏色衰退明顯且添加量過高導致染劑產生塊狀沉澱。從表6可知明膠作為高分子增稠劑於染髮劑中的添加量較佳為1至2.5wt%。 As shown in Table 6 below, when the amount of gelatin added is 1wt% and 2.5wt%, the color difference value and tinting strength of hair dyeing are similar, but when the addition amount is 5wt%, too much addition causes the dye to coagulate, and after coagulation into a block Dyeing effect decreased. After one washing, the color difference value and tinting strength of 1wt% and 2.5wt% did not decrease significantly, but after one washing of 5wt% gelatin, the color decline was obvious and the addition amount was too high, resulting in block precipitation of the dye. It can be seen from Table 6 that the addition amount of gelatin as a polymer thickener in the hair dye is preferably 1 to 2.5 wt %.
如下表7，***膠添加量為1wt%時，其染色效果無明顯變化，但是經過一次水洗時，顏色衰退明顯，與2.5wt%以及5wt%的添加相比，1wt%的***膠添加濃度太低，對於耐水洗的效果並沒有幫助，添加了2.5wt%的***膠染色效果沒有明顯的改變，但是與1wt%的相比，一次水洗的結果明顯較佳，表示濃度到達2.5wt%時，與界面活性劑以及染劑結合良好，添加到了5wt%時，雖然色差值以及著色力略為下降，但是經過一次水洗後，對於色差值以及著色力仍有保持。從表7可知，***膠作為高分子增稠劑於染髮劑中的添加量較佳為2.5wt%到5wt%。 As shown in Table 7 below, when the addition amount of gum arabic is 1wt%, the dyeing effect has no obvious change, but after one washing, the color decline is obvious. Low, it does not help the effect of washing resistance, the dyeing effect of adding 2.5wt% of gum arabic has no obvious change, but compared with 1wt%, the result of one washing is obviously better, indicating that when the concentration reaches 2.5wt%, It combines well with surfactants and dyes. When added to 5wt%, although the color difference value and tinting strength are slightly reduced, after one washing, the color difference value and tinting strength are still maintained. It can be seen from Table 7 that the addition amount of gum arabic as a polymer thickener in the hair dye is preferably 2.5 wt % to 5 wt %.
如下表8，1wt%至5wt%的羥乙基纖維素(HEC)添加量在染髮劑中 都具有穩定的色差值及著色力，而經過一次水洗後，殘餘的色差值及著色力在各個重量百分濃度也相近，表示羥乙基纖維素在1wt%的添加即可達到穩定的效果。從表8可知，羥乙基纖維素作為高分子增稠劑於染髮劑中的添加量可為1wt%到5wt%，較佳為1wt%。羥乙基纖維素添加後，毛髮染出的顏色為橘黃色。 The following table 8, 1wt% to 5wt% of hydroxyethyl cellulose (HEC) added in the hair dye Both have stable color difference value and tinting strength, and after one washing, the residual color difference value and tinting strength are also similar in each weight percentage concentration, indicating that the addition of 1wt% of hydroxyethyl cellulose can achieve stable color. Effect. It can be seen from Table 8 that the addition amount of hydroxyethyl cellulose as a polymer thickener in the hair dye can be 1 wt % to 5 wt %, preferably 1 wt %. After the addition of hydroxyethyl cellulose, the color of the hair dyed is orange.
實施例5：Example 5:
已知市售染髮液與市售染髮乳的平均黏度(cps)分別約為24.7cps與87.2cps；是以，為了使本發明天然染髮劑商品化為與市售產品相近的黏度以達成實用性，實施例5使用黏度計測試明膠以及***膠添加於漆酶催化植物酚酸染劑後的黏度增加情形，並與市售商品進行比對是否添加後有達成與市售相近的黏度。具體地，本發明天然染髮劑的商品化配方使用1至2.5wt%的明膠與2.5到 5wt%的***膠組合成高分子增稠劑，即天然染髮劑的商品化配方中的高分子增稠劑總添加量介於3.5至7.5wt%。藉此，測試前述明膠與***膠的組合加入漆酶催化植物酚酸染劑中，獲得如下表9所示的黏度。 It is known that the average viscosity (cps) of the commercially available hair dye and the commercially available hair dye is about 24.7cps and 87.2cps respectively; therefore, in order to commercialize the natural hair dye of the present invention to a viscosity similar to that of the commercially available product to achieve practicality , Example 5 Use a viscometer to test the viscosity increase after adding gelatin and gum arabic to the laccase-catalyzed plant phenolic acid dye, and compare it with a commercially available product to see if the added viscosity is similar to that of the commercially available product. Specifically, commercial formulations of natural hair dyes of the present invention use 1 to 2.5 wt % of gelatin with 2.5 to 2.5 wt % 5wt% of gum arabic is combined into polymer thickener, that is, the total amount of polymer thickener added in the commercial formulation of natural hair dye ranges from 3.5 to 7.5wt%. Thereby, the combination of the aforementioned gelatin and gum arabic was added to the laccase-catalyzed plant phenolic acid dye to obtain the viscosity shown in Table 9 below.
從表9結果可知，配方1至7的最低混合黏度為29.9cps，超過市售染髮液的黏度24.7cps，表示明膠與***膠混合後，可使天然染髮劑的商品化配方的黏度達到與市售染髮液的黏度下限；進而，配方1至7的最高混合黏度為79.6cps，最接近市售染髮乳黏度的87.2cps，表示明膠與***膠混合後，可使天然染髮劑的商品化配方的黏度達到與市售染髮乳的黏度上限相近，是以，明膠與***膠的混合能夠實現調整天然染髮劑的商品化配方的黏度達到期望值。 From the results in Table 9, it can be seen that the minimum mixing viscosity of formulations 1 to 7 is 29.9cps, which exceeds the viscosity of the commercially available hair dye solution by 24.7cps, indicating that the mixture of gelatin and gum arabic can make the commercial formulation of natural hair dyes. The lower limit of the viscosity of commercial hair dyes; furthermore, the highest mixed viscosity of formulas 1 to 7 is 79.6cps, which is closest to the viscosity of 87.2cps of commercially available hair dyes, indicating that after mixing gelatin and gum arabic, the commercial formulation of natural hair dyes can be reduced. The viscosity is close to the upper limit of the viscosity of the commercial hair dye, so the mixture of gelatin and gum arabic can adjust the viscosity of the commercial formulation of natural hair dye to the desired value.
實施例5進一步在漆酶催化植物酚酸染劑為20mM阿魏酸酚酸染劑添加氯化鈣，分別添加陽離子型界面活性劑5mM CTAB以及5.5mM CTAC的固定組成上，進一步分別添加1wt%明膠與2.5wt%***膠組合(黏度下限)以及2.5wt%明膠與5wt%***膠組合(黏度上限)的高分子增稠劑，以測試添加混合明膠及***膠的高分子增稠劑後，對染劑染色效果以及水洗效果的影響，如下表10所示。 In Example 5, the laccase catalyzed plant phenolic acid dye was 20mM ferulic acid phenolic acid dye and calcium chloride was added, and the cationic surfactant 5mM CTAB and 5.5mM CTAC were respectively added to the fixed composition, and 1wt% was further added respectively. The polymer thickeners of gelatin combined with 2.5wt% gum arabic (lower viscosity limit) and 2.5wt% gelatin combined with 5wt% gum arabic (upper viscosity limit) to test after adding the polymer thickener mixed with gelatin and gum arabic, The influence on the dyeing effect and washing effect of the dye is shown in Table 10 below.
表10：
由表10可知，無論是明膠1wt%與***膠2.5wt%之黏度下限組合或是明膠2.5wt%與***膠5wt%之黏度上限組合，兩種組合的染色結果相近，添加CTAB的色差值分別為64.31以及62.53，添加CTAC的色差值分別為62.17以及63.37，著色力的結果也是相近，添加CTAB的著色力為23.96以及22.56，添加CTAC的著色力為25.93以及24.82，表示無論是上限添加還是下限添加對於染色的效果是沒有太多的影響，顯示明膠與***膠混合的適用範圍為1至2.5wt%的明膠與2.5到5wt%的***膠，在這範圍中的黏度以及染色效果是可以被接受的。 It can be seen from Table 10 that whether it is the combination of the lower viscosity limit of 1wt% gelatin and gum arabic 2.5wt% or the upper viscosity limit combination of 2.5wt% gelatin and 5wt% gum arabic, the dyeing results of the two combinations are similar, and the color difference value of CTAB is added. They are 64.31 and 62.53 respectively. The color difference values of CTAC are 62.17 and 63.37, respectively. The results of tinting strength are also similar. The tinting strength of CTAB is 23.96 and 22.56, and the tinting strength of CTAC is 25.93 and 24.82. The addition of the lower limit does not have much effect on the effect of dyeing. It shows that the applicable range of mixing gelatin and gum arabic is 1 to 2.5wt% gelatin and 2.5 to 5wt% gum arabic. The viscosity and dyeing effect in this range are acceptable.
如表10所示，一次水洗後，色差值以及著色力的下降是不顯著的，無論是上限值的明膠2.5wt%、***膠5wt%或是下限的明膠1wt%、*** 膠2.5wt%，添加CTAB下限值色差值從64.31降至61.47，著色力從23.96降至22.15，上限值色差值從62.53降至58.92，著色力從22.56降至20.04，CTAC下限值色差值從62.17降至60.36，著色力從25.93降至22.43，上限值色差值從63.37降至59.82，著色力從24.82降至20.86，與單一添加高分子增稠劑的結果相近，表示了混合明膠與***膠的染劑是可用的，在明膠1至2.5wt%、***膠2.5至5wt%的黏度達到市售的標準且耐水洗的效果並沒有受到影響。 As shown in Table 10, after one wash, the color difference value and the coloring strength decreased not significantly, whether it is the upper limit of gelatin 2.5wt%, gum arabic 5wt% or the lower limit of gelatin 1wt%, arabic Adhesive 2.5wt%, adding CTAB lower limit color difference value decreased from 64.31 to 61.47, tinting strength decreased from 23.96 to 22.15, upper color difference value decreased from 62.53 to 58.92, tinting strength decreased from 22.56 to 20.04, CTAC lower limit The color difference value decreased from 62.17 to 60.36, the tinting strength decreased from 25.93 to 22.43, the upper limit color difference value decreased from 63.37 to 59.82, and the tinting strength decreased from 24.82 to 20.86, which is similar to the result of adding a single polymer thickener. It is shown that a dye mixed with gelatin and acacia is available, and the viscosity of gelatin 1 to 2.5 wt% and acacia 2.5 to 5 wt% reaches the commercial standard and the effect of washing resistance is not affected.
實施例6：Example 6:
維生素C可以提供電子還原自由基成較穩定之自由基或化合物，以降低氧化傷害，故實施例6使用維生素C作為抗氧化劑。基於實施例1至4的結果，實施例6在漆酶催化植物酚酸染劑為20mM阿魏酸酚酸染劑添加氯化鈣，分別添加陽離子型界面活性劑5mM CTAB以及5.5mM CTAC的固定組成上，進一步分別添加0.1wt%、0.2wt%、0.25wt%、0.3wt%以及0.5wt%的維生素C，對漂白的毛髮進行染色30分鐘，以測試維生素C對染劑染色效果以及水洗效果的影響，如下表11所示。 Vitamin C can provide electrons to reduce free radicals into more stable free radicals or compounds to reduce oxidative damage, so Example 6 uses vitamin C as an antioxidant. Based on the results of Examples 1 to 4, in Example 6, the laccase-catalyzed plant phenolic acid dye was 20 mM ferulic acid phenolic acid dye added with calcium chloride, and the cationic surfactant 5 mM CTAB and 5.5 mM CTAC were added for fixation. In terms of composition, 0.1wt%, 0.2wt%, 0.25wt%, 0.3wt% and 0.5wt% of vitamin C were further added, and the bleached hair was dyed for 30 minutes to test the dyeing effect of vitamin C on the dye and the washing effect. , as shown in Table 11 below.
由表11可知，維生素C的添加量在0.1至0.25wt%時，染色的效果是相近的，但是當維生素C添加量為0.3wt%開始，頭髮染色的色差值以及著色力出現下降，毛髮染色後顏色變為黃橘色，顏色受到還原，表示維生素C的添加量為0.1至0.25wt%時是適合被添加的，且對於色差值以及著色力是沒有明顯的改變。 It can be seen from Table 11 that when the addition amount of vitamin C is 0.1 to 0.25 wt%, the dyeing effect is similar, but when the addition amount of vitamin C is 0.3 wt%, the color difference value and coloring power of hair dyeing decrease, and the hair is dyed. After dyeing, the color changes to yellow-orange, and the color is reduced, indicating that the addition amount of vitamin C is 0.1 to 0.25 wt%, which is suitable to be added, and there is no obvious change in the color difference value and tinting strength.
實施例7：Example 7:
實施例7在漆酶催化植物酚酸染劑為20mM阿魏酸酚酸染劑添加氯化鈣，分別添加陽離子型界面活性劑5mM CTAB以及5.5mM CTAC的固定組成上，分別添加0.1wt%、0.2wt%、0.25wt%的維生素C，並以波長為254nm的UV燈，對染色後的毛髮照射7日並在第1、3、5、7日取出並使用色差儀讀取色差(△E)與著色力(K/S)值的變化量，以測試添加維生素C後，UV光照對染髮顏色衰退程度的影響，如下表12所示。 Example 7 The laccase catalyzed plant phenolic acid dye was 20 mM ferulic acid phenolic acid dye added with calcium chloride, and the cationic surfactant 5 mM CTAB and 5.5 mM CTAC were added to the fixed composition, respectively adding 0.1wt%, 0.2wt%, 0.25wt% of vitamin C, and with a UV lamp with a wavelength of 254nm, the hair after dyeing was irradiated for 7 days and taken out on the 1st, 3rd, 5th and 7th days and used a color difference meter to read the color difference (△E ) and the change in the tinting strength (K/S) value to test the effect of UV light on the color fade of dyed hair after adding vitamin C, as shown in Table 12 below.
由表12可知，沒有添加維生素C的阿魏酸酚酸染劑(FA+Ca)在第一天照光即失去效果，顏色產生明顯衰退，添加了維生素C的染劑在第一天UV 光的照射下，色差值並無明顯的衰退，表示毛髮受到維生素C的保護使得顏色表現與剛染色的結果相近，經過七日的照光後，添加了維生素C毛髮的色差值下降幅度緩慢，而沒有添加維生素C的頭髮可以發現色差值明顯下降，色差值從59.73降至35.75，顏色受到光照產生明顯的衰退，表示添加了維生素C的頭髮在接受照光時，維生素C是有起到保護的效果使得顏色不會產生明顯變化。 As can be seen from Table 12, the ferulic acid phenolic acid dye (FA+Ca) without adding vitamin C loses its effect on the first day, and the color declines significantly, and the dye adding vitamin C is UV on the first day. Under the irradiation of light, the color difference value has no obvious decline, which means that the hair is protected by vitamin C, so that the color performance is similar to the result of just dyeing. After seven days of illumination, the color difference value of the hair added with vitamin C decreases slowly. , while the hair with no vitamin C added can find that the color difference value has dropped significantly, the color difference value has dropped from 59.73 to 35.75, and the color has been significantly degraded by light, which means that the hair with added vitamin C is exposed to light. To the protective effect, the color will not change significantly.
實施例8：Example 8:
實施例8在漆酶催化植物酚酸染劑為20mM阿魏酸酚酸染劑添加氯化鈣(FA+Ca)的固定組成上，進一步添加陽離子型界面活性劑(5mM CTAB、5.5mM CTAC)、高分子增稠劑(混合1至2.5wt%的明膠(GE)以及2.5至5wt%的***膠(GA))以及0.1至0.25wt%的維生素C(縮寫VC)，組成本發明天然染髮劑的商品化配方。實施例8對前述商品化配方染髮劑染色後的毛髮進行30次的水洗，每次水洗時間為10分鐘，使用100rpm轉速的磁石攪拌器模擬洗髮的過程，以測試商品化配方染髮劑是否達到商品化的需求。於本實施例中，漂白頭髮的CIE L*a*b*色度空間參數值如下：L*值為79.08，a*值為2.34，b*值為25.72，色相角(h°)為84.79。測試結果如下表13所示。 Example 8 On the fixed composition of the laccase-catalyzed plant phenolic acid dye being 20mM ferulic acid phenolic acid dye and adding calcium chloride (FA+Ca), a cationic surfactant (5mM CTAB, 5.5mM CTAC) was further added , polymer thickener (mix 1 to 2.5wt% of gelatin (GE) and 2.5 to 5wt% of gum arabic (GA)) and 0.1 to 0.25wt% of vitamin C (abbreviated as VC) to form the natural hair dye of the present invention commercial formulation. Example 8 The hair dyed with the aforementioned commercial formula hair dye was washed 30 times, and the time for each washing was 10 minutes, and the process of shampooing was simulated using a magnetic stirrer with a rotating speed of 100 rpm to test whether the commercial formula hair dye reached commoditization needs. In this embodiment, the CIE L*a*b* chromaticity space parameter values of bleached hair are as follows: L* value is 79.08, a* value is 2.34, b* value is 25.72, and hue angle (h°) is 84.79. The test results are shown in Table 13 below.
由表13至表15可知，未添加配方的阿魏酸染劑(FA+Ca)在經過一次水洗後顏色無法保持而脫落，色差值從55.49降至43.85，著色力從16.44降至10.57，毛髮顏色從橘紅色衰退為黃色，水洗到第十次時顏色幾乎脫落，毛髮顏色趨於白色，表示沒有界面活性劑與高分子增稠劑結合的毛髮耐水洗的效果不彰，添加了配方的染劑在水洗結果可以發現，經過一次水洗後顏色沒有明顯的變化，色差值以及著色力衰退較少，添加CTAB的配方色差值分別57.29降至54.43以及63.2降至62.34，而著色力從21.39降至20.51以及25.75降至22.23，添加CTAC的配方色差值從59.84降至55.58以及59.71降至57.97，著色力從22.65降至21.12以及23.03降至21.35，與未添加的阿魏酸染劑相比，色差值與著色力在一次水洗後仍能保持。 It can be seen from Table 13 to Table 15 that the color of the ferulic acid dye (FA+Ca) without the formula can not be maintained and fell off after one washing, the color difference value decreased from 55.49 to 43.85, and the tinting strength decreased from 16.44 to 10.57. The color of the hair declines from orange to yellow, and the color almost falls off after the tenth wash, and the color of the hair tends to be white, indicating that the hair without the combination of surfactants and polymer thickeners has poor washing resistance. It can be found in the washing results of the dye that after one washing, the color has no obvious change, and the color difference value and tinting strength decline less. 21.39 to 20.51 and 25.75 to 22.23, the color difference value of the formula with CTAC added from 59.84 to 55.58 and 59.71 to 57.97, the tinting strength from 22.65 to 21.12 and 23.03 to 21.35, which is similar to the unadded ferulic acid dye. In contrast, the color difference value and tinting strength can still be maintained after one wash.
含添加物的染劑經過水洗30次後，與沒添加物的染劑相比有明顯的不同，含添加物的染劑經水洗30次的毛髮顏色呈現為橘黃色的顏色，而沒添加物的染劑染出的毛髮顏色已經轉為白色，且色差值以及著色力下降僅剩下15.84以及3.52，顏色幾乎脫落，含添加物的染劑的頭髮顏色具有橘黃色的顏色，色差值僅下降至45左右，而著色力仍保持在10以上，表示含添加物的染劑對於多次的水洗具有抵抗的作用，而從染色後尚未水洗的效果可以發現著色力是有明顯的上升，頭髮的顏色變深，可以得出含添加物的染劑也具有幫助頭髮染色的效果。 After 30 washes of the dye with additives, compared with the dye without additives, the hair color of the dye with additives after washing 30 times is orange, but without additives. The color of the hair dyed by the dye has turned white, and the color difference value and the tinting strength have dropped to only 15.84 and 3.52, and the color has almost fallen off. The hair color of the dye containing additives has an orange color, and the color difference value It only dropped to about 45, but the tinting strength remained above 10, indicating that the dye containing additives has resistance to multiple washings, and from the effect of not washing after dyeing, it can be found that the tinting strength has increased significantly. The color of the hair becomes darker, and it can be concluded that the dye containing additives also has the effect of helping the hair color.
實施例9：Example 9:
實施例9在漆酶催化植物酚酸染劑為20mM阿魏酸酚酸染劑添加氯化鈣(FA+Ca)的固定組成上，進一步添加陽離子型界面活性劑(5mM CTAB、 5.5mM CTAC)、高分子增稠劑(混合1至2.5wt%的明膠(GE)以及2.5至5wt%的***膠(GA))以及0.1至0.25wt%的維生素C(縮寫VC)，組成本發明天然染髮劑的商品化配方。實施例9對前述商品化配方染髮劑染色後的毛髮，以15W的UV燈連續照射30日，以測試UV光照對商品化配方染髮顏色衰退程度的影響。於本實施例中，漂白頭髮的CIE L*a*b*色度空間參數值如下：L*值為78.48，a*值為2.68，b*值為26.57，色相角(h°)為84.24。測試結果如下表16至表18所示。 Example 9 On the fixed composition of the laccase-catalyzed plant phenolic acid dye being 20mM ferulic acid phenolic acid dye and adding calcium chloride (FA+Ca), a cationic surfactant (5mM CTAB, FA+Ca) was further added. 5.5mM CTAC), polymeric thickener (mixing 1 to 2.5wt% of gelatin (GE) and 2.5 to 5wt% of gum arabic (GA)) and 0.1 to 0.25wt% of vitamin C (abbreviated VC), consisting of Invented commercial formulations of natural hair dyes. Example 9 The hair dyed with the aforementioned commercial formula hair dye was continuously irradiated with a 15W UV lamp for 30 days to test the effect of UV light on the color decay degree of the commercial formula hair dyed hair. In this embodiment, the CIE L*a*b* chromaticity space parameter values of bleached hair are as follows: L* value is 78.48, a* value is 2.68, b* value is 26.57, and hue angle (h°) is 84.24. The test results are shown in Tables 16 to 18 below.
由上列表16至表18可知，毛髮經過UV光照射30日後，發現無添加物染劑配方染色後毛髮色差值與著色力明顯下降，在照射第一天時就失去了染色的效果，到了第20日後，色差值下降趨於平緩，而頭髮的顏色從橘紅色衰退至黃橘色，且著色力在第30日後下降到10以下，表示頭髮對於UV光的照射的抵抗能力不佳。反觀含添加物染劑配方染色後毛髮經過30日的照射後，色差值以及著色力保持較為穩定，頭髮的顏色無明顯的變化，仍呈現橘紅色的顏色，表示含添加物染劑配方染色後毛髮對於UV光照射具有抵抗的能力。 From Table 16 to Table 18 above, it can be seen that after 30 days of UV light irradiation on the hair, it is found that the color difference value and coloring strength of the hair after dyeing with the additive-free dye formula are significantly reduced, and the dyeing effect is lost on the first day of irradiation. After the 20th day, the color difference value decreased gradually, while the color of the hair declined from orange-red to yellow-orange, and the tinting strength dropped to below 10 after the 30th day, indicating that the hair had poor resistance to UV light irradiation. On the other hand, after 30 days of irradiation, the color difference value and tinting strength of the hair after dyeing with the additive-containing dye formula remained relatively stable, and the color of the hair did not change significantly, but still showed an orange-red color, indicating that the additive-containing dye formula was dyed The back hair is resistant to UV light exposure.
實施例10：Example 10:
實施例10在漆酶催化植物酚酸染劑為20mM阿魏酸酚酸染劑添加氯化鈣(FA+Ca)的固定組成上，進一步添加陽離子型界面活性劑(5mM CTAB、5.5mM CTAC)、高分子增稠劑(混合1至2.5wt%的明膠(GE)以及2.5至5wt%的***膠(GA))以及0.1至0.25wt%的維生素C(縮寫VC)，組成本發明天然染髮劑的商品化配方。如表19所示，實施例10在拉伸速率為50mm/min，頭髮測試的標點距離為100mm，髮束條件為截面長10mm，厚度測量為0.15mm，進行三次測試並取平均值等條件下，測試以本發明商品化配方染髮後的毛髮斷裂強度(MPa)，測試結果如下表19所示。 Example 10 On the fixed composition of the laccase-catalyzed plant phenolic acid dye being 20mM ferulic acid phenolic acid dye and adding calcium chloride (FA+Ca), a cationic surfactant (5mM CTAB, 5.5mM CTAC) was further added , polymer thickener (mix 1 to 2.5wt% of gelatin (GE) and 2.5 to 5wt% of gum arabic (GA)) and 0.1 to 0.25wt% of vitamin C (abbreviated as VC) to form the natural hair dye of the present invention commercial formulation. As shown in Table 19, in Example 10, the tensile rate is 50 mm/min, the punctuation distance of the hair test is 100 mm, the condition of the hair bundle is that the section length is 10 mm, the thickness measurement is 0.15 mm, and three tests are carried out and the average value is obtained. , test the hair breaking strength (MPa) after dyeing with the commercial formulation of the present invention, and the test results are shown in Table 19 below.
由表19可知，毛髮在經過漂白後，結構受到破壞使毛髮變得脆 弱，斷裂強度急速下降，原先毛髮的斷裂力為204.8MPa，經過漂白後下降至117.0MPa，在經過阿魏酸酚酸的染色後發現頭髮的斷裂力與經過漂白的頭髮相近，為126.7MPa，表示使用漆酶催化植物酚酸染劑染髮無法幫助毛髮的修復；當毛髮使用添加了下限值(5mM CTAB(0.18wt%)或5.5mM CTAC(0.18wt%)、2.5wt%***膠、1wt%明膠、0.1wt%維生素C)配方的染劑後，毛髮的斷裂強度有所上升，從126.7上升至163.4以及157.7，進而添加了上限值(5mM CTAB或5.5mM CTAC、5wt%***膠、2.5wt%明膠、0.25wt%維生素C)配方的染劑後，毛髮的斷裂強度上升為164.6以及165.6，顯示毛髮經過了本發明商品化配方染劑染色後，毛髮物理性質的斷裂強度上有所改善，而從添加的濃度可以發現改變增稠劑或是維生素C的含量對頭髮的斷裂力無明顯的影響，上下限值接近。 It can be seen from Table 19 that after the hair is bleached, the structure is damaged and the hair becomes brittle Weak, the breaking strength drops rapidly, the breaking force of the original hair is 204.8MPa, and after bleaching, it drops to 117.0MPa. After dyeing with ferulic acid phenolic acid, it is found that the breaking force of the hair is similar to that of the bleached hair, which is 126.7MPa. Indicates that the use of laccase to catalyze the use of plant phenolic acid dyes to dye hair cannot help hair repair; when the hair is added with a lower limit (5mM CTAB (0.18wt%) or 5.5mM CTAC (0.18wt%), 2.5wt% gum arabic, 1wt % gelatin, 0.1wt% vitamin C) formula, the breaking strength of hair increased from 126.7 to 163.4 and 157.7, and then added the upper limit (5mM CTAB or 5.5mM CTAC, 5wt% gum arabic, 2.5wt% gelatin, 0.25wt% vitamin C) formula, the breaking strength of the hair increased to 164.6 and 165.6, showing that after the hair was dyed with the commercial formula dye of the present invention, the breaking strength of the physical properties of the hair increased. From the added concentration, it can be found that changing the content of thickener or vitamin C has no obvious effect on the breaking force of hair, and the upper and lower limits are close.
Claims (9)
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| CN1197544C (en) * | 2003-03-18 | 2005-04-20 | 张雪松 | Hair dyeing agent using rutin or guercetin as dyestuff |
| CN102686209A (en) * | 2009-12-21 | 2012-09-19 | 富士胶片株式会社 | Hair dye |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1197544C (en) * | 2003-03-18 | 2005-04-20 | 张雪松 | Hair dyeing agent using rutin or guercetin as dyestuff |
| CN102686209A (en) * | 2009-12-21 | 2012-09-19 | 富士胶片株式会社 | Hair dye |
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| Title |
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| Jong-Rok Jeon,Eun-Ju Kim,Kumarasamy Murugesan,Hyo-Keun Park,Young-Mo Kim,Jung-Hee Kwon,Wang-Gi Kim,Ji-Yeon Lee,Yoon-Seok Chang，Laccase-catalysed polymeric dye synthesis from plant-derived phenols for potential application in hair dyeing: Enzymatic colourations driven by homo- or hetero-polymer synthesis，Microbial Biotechnology (2010) 3(3), 324–335 * |
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