CN113499273B - Hair dye containing salidroside nanoparticles and preparation method and application method thereof - Google Patents

Hair dye containing salidroside nanoparticles and preparation method and application method thereof Download PDF

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CN113499273B
CN113499273B CN202110874306.XA CN202110874306A CN113499273B CN 113499273 B CN113499273 B CN 113499273B CN 202110874306 A CN202110874306 A CN 202110874306A CN 113499273 B CN113499273 B CN 113499273B
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salidroside
hair
deionized water
hair dye
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CN113499273A (en
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张键华
李昊天
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Chengdu Juyuan Zhixin Technology Co.,Ltd.
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Shaoxing Fuyuan Biotechnology Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • A61K8/602Glycosides, e.g. rutin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52Stabilizers
    • A61K2800/522Antioxidants; Radical scavengers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/82Preparation or application process involves sonication or ultrasonication

Abstract

The invention discloses a hair dye containing salidroside nano particles, a preparation method and a using method thereof, wherein the hair dye comprises the following components: the dye comprises an agent A containing a dye and an agent B containing an oxidant, wherein the agent A contains 5, 6-dihydroxyindole and salidroside nanoparticles, and the weight ratio of the 5, 6-dihydroxyindole to the salidroside nanoparticles is 1-8:0.5-4. The salidroside nanoparticle, especially the salidroside nanoparticle prepared by ultrasonic method, is added into the hair dye taking 5, 6-dihydroxyindole as the intermediate of the dye, so that the reducibility of the hair dye can be effectively improved, the consumption of the reducing agent required by long-term storage of the hair dye can be effectively reduced, and the time for dyeing hair can be shortened.

Description

Hair dye containing salidroside nanoparticles and preparation method and application method thereof
Technical Field
The invention relates to the technical field of hair dyes, in particular to a hair dye containing salidroside nanoparticles, a preparation method and a use method thereof.
Background
Hair dyeing is one of the most common means for people to change their image, and hair dye, which is an article with a color-changing effect, is beginning to become a daily necessity for more and more people. Human hair consists of three parts, namely an epidermis scale layer, a cortex layer and a medulla layer. The outermost layer is a semitransparent or colorless epidermis scale layer; the cortex layer is the part for depositing melanin synthesized by human body, and the inner layer is the medulla layer. The amount of melanin deposition in the cortical layer determines the difference of color development and is also a core part in the dyeing process. The indole substances easily penetrate into hair and enter into the cortex layer of the hair, and macromolecule colored substances are formed by oxidative polymerization and fixed in the hair, and the oxidation condition is mild. Since 5, 6-dihydroxyindole itself is a substance produced by living organisms, it is free from toxic and side effects, and is an important intermediate for synthesizing melanin, and it has been used for substituting aniline and phenol compounds in some washing products. The existing artificial melanin hair dye has active 5, 6-dihydroxyindole, is easily oxidized into indole quinone by air, and can greatly oxidize hydroxyl groups when the polymerization plays a role of dyeing black. The disappearance of the hydroxyl active site weakens the binding force between the hydroxyl active site and the micromolecular pigment, which can seriously affect the dyeing efficiency and effect in the field of color dyeing, so that the micromolecule cannot be dyed and fixed in the hair, the color can be obviously changed into pure black after washing for several times, the time required for dyeing is usually longer (more than 30 minutes) to ensure the color dyeing effect, and the practical application of the hair dye is greatly affected; meanwhile, 5, 6-dihydroxyindole is extremely easy to oxidize by air, a large amount of reducing agent is forced to be added during preservation, and the 5, 6-dihydroxyindole contradicts with the oxidative polymerization of indole, so that the time required for dyeing hair is further prolonged, and the reducing agent consumption during preservation is particularly important.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a hair dye containing salidroside nano particles, a preparation method and a use method thereof, and the hair dye solves the problem that a large amount of reducing agent is added during preservation in order to prevent 5, 6-dihydroxyindole from being oxidized by air in the prior art.
The technical scheme for solving the technical problems is as follows: provided is a hair dye containing salidroside nanoparticles, comprising: the dye comprises an agent A containing a dye and an agent B containing an oxidant, wherein the agent A contains 5, 6-dihydroxyindole and salidroside nanoparticles, and the weight ratio of the 5, 6-dihydroxyindole to the salidroside nanoparticles is 1-8:0.5-4.
The beneficial effects of the invention are as follows: the hair dyeing process is to firstly open the hair flake at the outermost layer of the hair, enable the matrix containing the coloring agent and the matrix containing the oxidizing agent to enter the hair through the small holes opened by the hair flake, bleach the pigment in the hair by the oxidizing agent, then perform oxidation reaction with the simultaneously entered coloring agent to re-color the hair, and finally close the hair flake, so that the hair is dyed with a new color. The agent A contains 5, 6-dihydroxyindole and salidroside nanoparticles, and the salidroside is prepared into nanoparticles, so that the particle size is small, the biocompatibility is good, the salidroside is easy to attach on the surface of hair, and the oxidation resistance of the salidroside can be enhanced, thereby solving the problem that a large amount of reducing agents are needed when the hair dye containing 5, 6-dihydroxyindole is stored for a long time. Meanwhile, the high specific surface area of the salidroside nanoparticle can realize quick dyeing within a few minutes, and the dyeing time is obviously reduced. In addition, the salidroside has good anti-ultraviolet capability, and can enhance the anti-ultraviolet and light protection effects of black hair after being introduced into the hair dye.
Based on the technical scheme, the invention can also be improved as follows:
the agent A consists of the following components in percentage by mass: 1-8% of 5, 6-dihydroxyindole, 0.5-4% of salidroside nano particles, 1-3% of isohexadecane, 1-3% of PPG-14 butyl ether, 6-12% of oleic acid, 6-12% of glycerol, 6-12% of butanediol, 4-8% of sodium sulfite, 4-8% of ethylhexyl methoxycinnamate, 2-6% of cetyl PEG, 0.5-4% of NaOH, 0.5-1% of orange pigment and the balance of deionized water;
the agent B consists of the following components in percentage by mass: 18-26% of hydrogen peroxide, 12-18% of oleyl alcohol, 12-18% of oleic acid, 12-18% of propylene glycol, 12-18% of isopropanol, 2-4% of sodium dodecyl sulfate, 1-2% of hydrated silica, and the balance of deionized water, wherein the pH is adjusted to 2.5-3.5 by phosphoric acid.
The beneficial effects of adopting the further technical scheme are as follows: the hair dye provided by the invention comprises two agents, namely an agent A and an agent B, which are independently packaged, wherein the agent A is a matrix containing a dye, comprises a dye intermediate, and also comprises an ultraviolet absorbent ethylhexyl methoxycinnamate, and simultaneously comprises an emulsifying agent, cetyl PEG serving as an permeation assisting agent and an auxiliary agent capable of preparing the cetyl PEG into a water phase and an oil phase, wherein the ethylhexyl methoxycinnamate is a good absorbent in an ultraviolet UVB region, and the reasonable compatibility and the introduction of the ethylhexyl methoxycinnamate also enable the dyed hair to have good ultraviolet protection effect and reduce the natural black light protection function, which is not provided by the traditional dye paste; the agent B contains an oxidant and also contains an aqueous phase and oil phase basic component, so that the agent B can form paste, and the matrix can oxidize the dye intermediate into macromolecular dye. The invention combines the A agent containing specific components with the specific B agent, can obviously reduce the dyeing time, and has good ultraviolet protection effect.
Further, the agent A consists of the following components in percentage by mass: 1-5% of 5, 6-dihydroxyindole, 0.5-2% of salidroside nano particles, 1-3% of isohexadecane, 1-3% of PPG-14 butyl ether, 6-8% of oleic acid, 8-12% of glycerin, 8-12% of butanediol, 4-6% of sodium sulfite, 6-8% of ethylhexyl methoxycinnamate, 4-6% of cetyl PEG, 0.5-1% of NaOH, 0.5-1% of orange pigment and the balance of deionized water;
the agent B consists of the following components in percentage by mass: 20-26% of hydrogen peroxide, 15-18% of oleyl alcohol, 12-15% of oleic acid, 12-15% of propylene glycol, 15-18% of isopropanol, 2-4% of sodium dodecyl sulfate, 1-2% of hydrated silica, and the balance of deionized water, wherein the pH is adjusted to 2.5-3.5 by phosphoric acid.
Further, the agent A consists of the following components in percentage by mass: 5, 6-dihydroxyindole 5%, salidroside nanoparticle 2%, isohexadecane 3%, PPG-14 butyl ether 3%, oleic acid 6%, glycerol 12%, butanediol 12%, sodium sulfite 4%, ethylhexyl methoxycinnamate 8%, cetyl PEG 6%, naOH0.5%, orange pigment 0.5%, and deionized water in balance;
the agent B consists of the following components in percentage by mass: hydrogen peroxide 20%, oleyl alcohol 18%, oleic acid 12%, propylene glycol 12%, isopropyl alcohol 18%, sodium dodecyl sulfonate 3%, hydrated silica 1%, phosphoric acid to adjust the pH to 3, and the balance deionized water.
Further, the salidroside nanoparticle is prepared by the following method: fully dissolving salidroside monomer powder in deionized water, adding horseradish peroxidase solution, stirring uniformly, performing ultrasonic treatment with ultrasonic frequency of 350-450W,35-45kHz, ultrasonic temperature of 40-50 ℃ and ultrasonic time of 3-5h, centrifuging after ultrasonic treatment, and washing.
The beneficial effects of adopting the further technical scheme are as follows: the invention adopts horseradish peroxidase and ultrasonic conditions to promote the polymerization of salidroside monomers, under the specific ultrasonic conditions, tiny bubbles in liquid vibrate under the action of an ultrasonic field to grow and continuously gather the energy of the ultrasonic field, when the energy reaches a threshold value, cavitation bubbles rapidly collapse and close, the service life of the cavitation bubbles is about 0.1 mu s, and the cavitation bubbles can release huge energy when rapidly collapsing, generate microjet with the speed of about 110m/s and strong impact force, so that the collision density is up to 1.5kg/cm 2 . Cavitation bubbles generate local high temperature and high pressure at the instant of rapid collapse, so that water generates active oxygen free radicals, and polymerization of salidroside monomers is initiated under the catalysis of horseradish peroxidase to form salidroside nanoparticlesThe rice grains have better antioxidation capability, can effectively prevent the 5, 6-dihydroxyindole from being oxidized, and further improve the dyeing effect of the hair dye.
Further, the concentration of the horseradish peroxidase solution is 8-12mg/mL, and the weight ratio of the salidroside monomer powder to the horseradish peroxidase is 20-30:1.
Further, the ultrasonic frequency was 400W,40kHz, the ultrasonic temperature was 45℃and the ultrasonic time was 4 hours.
The preparation method of the hair dye containing the salidroside nano-particles comprises the following steps:
s1, preparing an A agent
S101, mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 50-80 ℃ to obtain a water phase;
s102, mixing and heating isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG to 50-80 ℃ to obtain an oil phase;
s103, adding the oil phase into the water phase, stirring, preserving heat at 50-80 ℃ for 10-20min, then adding 5, 6-dihydroxyindole, salidroside nanoparticles and orange pigment, stirring for 5-10min, and regulating the pH value to 9-11 by using NaOH to prepare an agent A;
s2, preparation of agent B
S201, mixing deionized water, propylene glycol, sodium dodecyl sulfonate and hydrated silica, and heating to 50-80 ℃ to obtain a water phase;
s202, mixing oleyl alcohol, oleic acid and isopropanol, and heating to 50-80 ℃ to obtain an oil phase;
s203, adding the oil phase into the water phase, stirring, preserving heat for 10-20min at 50-80 ℃, then adding hydrogen peroxide, and regulating the pH value to 2-4 by using phosphoric acid to prepare the agent B.
The beneficial effects of the invention are as follows: in the agent A, the aqueous phase component and the oil phase component are mixed and emulsified to form the dye paste, and if the proportion of the components in the emulsifier and the aqueous phase oil phase is out of balance, the dye paste is demulsified, and the aqueous phase and the oil phase are separated, so that the dyeing effect is affected. Similarly, the agent B contains an oxidant and also contains a water phase oil phase basic component, and the water phase and the oil phase are mixed to form paste matched with the agent A, so that the coloring agent in the agent A can be effectively oxidized, and the hair can be re-colored.
Further, the temperature is heated to 60 ℃ in steps S101 and S102, and the heat-insulating temperature is 60 ℃ in step S103.
Further, the temperature is heated to 60 ℃ in steps S201 and S202, and the heat-insulating temperature is 60 ℃ in step S203.
The application method of the hair dye containing the salidroside nano-particles comprises the following steps: mixing agent A and agent B at a mass ratio of 1-2:1-2, applying on hair, and cleaning hair after 8-12 min.
Further, uniformly mixing the agent A and the agent B according to the mass ratio of 1:1, applying the mixture on hair, and cleaning the hair after 10 minutes.
The invention has the following beneficial effects:
the salidroside nanoparticle, especially the salidroside nanoparticle prepared by ultrasonic method, is added into the hair dye taking 5, 6-dihydroxyindole as the intermediate of the dye, so that the reducibility of the hair dye can be effectively improved, the consumption of the reducing agent required by long-term storage of the hair dye can be effectively reduced, and the time for dyeing hair can be shortened.
Drawings
FIG. 1 is a scanning electron microscope image of salidroside nanoparticles.
Detailed Description
The examples given below are only intended to illustrate the invention and are not intended to limit the scope thereof. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
a hair dye containing salidroside nanoparticles, comprising: agent A and agent B;
the agent A consists of the following components in percentage by mass: 1% of 5, 6-dihydroxyindole, 0.5% of salidroside nano particles, 1% of isohexadecane, 1% of PPG-14 butyl ether, 6% of oleic acid, 6% of glycerin, 6% of butanediol, 4% of sodium sulfite, 4% of ethylhexyl methoxycinnamate, 2% of cetyl PEG, 0.5% of NaOH, 0.5% of orange pigment and the balance of deionized water;
wherein, the salidroside nano-particles are prepared by the following method: 75mg of salidroside monomer powder is fully dissolved in 25mL of deionized water, 300uL of horseradish peroxidase solution (8 mg/mL) is added, an ultrasonic probe is immersed in the reaction solution after uniform stirring, the probe is adjusted to a working state (350W, 45 kHz), ultrasonic treatment is carried out on the reaction solution, the reaction solution is operated in a pulse mode of 1.6s on/0.4 s off, a water bath device is additionally added to maintain the reaction system at 40 ℃, after 5h ultrasonic treatment, the reaction system is gradually changed from colorless and transparent to turbid, the obtained solution is rapidly subjected to centrifugal treatment (15000 r/min,8 min), and the obtained precipitate is washed three times by deionized water, so as to obtain the salidroside nanoparticle.
The agent B consists of the following components in percentage by mass: 18% of hydrogen peroxide, 12% of oleyl alcohol, 12% of oleic acid, 12% of propylene glycol, 12% of isopropanol, 1% of sodium dodecyl sulfonate, 1% of hydrated silica, and the balance of deionized water.
The preparation method of the hair dye containing the salidroside nano-particles comprises the following steps:
s1, preparing an A agent
S101, mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 50 ℃ to obtain a water phase;
s102, mixing and heating isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG to 50 ℃ to obtain an oil phase;
s103, adding the oil phase into the water phase, stirring, preserving heat at 50 ℃ for 10min, then adding 5, 6-dihydroxyindole, salidroside nanoparticles and orange pigment, stirring for 5min, and regulating the pH value by using NaOH to prepare an agent A;
s2, preparation of agent B
S201, mixing deionized water, propylene glycol, sodium dodecyl sulfonate and hydrated silica, and heating to 80 ℃ to obtain a water phase;
s202, mixing oleyl alcohol, oleic acid and isopropanol, and heating to 50 ℃ to obtain an oil phase;
s203, adding the oil phase into the water phase, stirring, preserving heat for 10min at 50 ℃, then adding hydrogen peroxide, and regulating the pH to 3 by using phosphoric acid to prepare the agent B.
Example 2:
a hair dye containing salidroside nanoparticles, comprising: agent A and agent B;
the agent A consists of the following components in percentage by mass: 8% of 5, 6-dihydroxyindole, 4% of salidroside nano particles, 3% of isohexadecane, 3% of PPG-14 butyl ether, 12% of oleic acid, 12% of glycerin, 12% of butanediol, 8% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG, 4% of NaOH, 1% of orange pigment and the balance of deionized water;
wherein, the salidroside nano-particles are prepared by the following method: 75mg of salidroside monomer powder is fully dissolved in 25mL of deionized water, 300uL of horseradish peroxidase solution (12 mg/mL) is added, an ultrasonic probe is immersed in the reaction solution after uniform stirring, the probe is adjusted to a working state (450W, 35 kHz), ultrasonic treatment is carried out on the reaction solution, the reaction solution is operated in a pulse mode of 1.6s on/0.4 s off, a water bath device is additionally added to maintain the reaction system at 50 ℃, after 3h ultrasonic treatment, the reaction system is gradually changed from colorless and transparent to turbid, the obtained solution is rapidly subjected to centrifugal treatment (15000 r/min,8 min), and the obtained precipitate is washed three times by the deionized water, so as to obtain the salidroside nanoparticle.
The agent B consists of the following components in percentage by mass: 26% of hydrogen peroxide, 18% of oleyl alcohol, 18% of oleic acid, 18% of propylene glycol, 18% of isopropanol, 2% of sodium dodecyl sulfonate, 2% of hydrated silica, and the balance of deionized water.
The preparation method of the hair dye containing the salidroside nano-particles comprises the following steps:
s1, preparing an A agent
S101, mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 80 ℃ to obtain a water phase;
s102, mixing and heating isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG to 80 ℃ to obtain an oil phase;
s103, adding the oil phase into the water phase, stirring, preserving heat at 80 ℃ for 20min, then adding 5, 6-dihydroxyindole, salidroside nanoparticles and orange pigment, stirring for 10min, and regulating the pH value by using NaOH to prepare an agent A;
s2, preparation of agent B
S201, mixing deionized water, propylene glycol, sodium dodecyl sulfonate and hydrated silica, and heating to 80 ℃ to obtain a water phase;
s202, mixing oleyl alcohol, oleic acid and isopropanol, and heating to 80 ℃ to obtain an oil phase;
s203, adding the oil phase into the water phase, stirring, preserving heat for 20min at 80 ℃, then adding hydrogen peroxide, and regulating the pH to 3 by using phosphoric acid to prepare the agent B.
Example 3:
a hair dye containing salidroside nanoparticles, comprising: agent A and agent B;
the agent A consists of the following components in percentage by mass: 1% of 5, 6-dihydroxyindole, 0.5% of salidroside nano particles, 1% of isohexadecane, 1% of PPG-14 butyl ether, 6% of oleic acid, 8% of glycerin, 8% of butanediol, 4% of sodium sulfite, 6% of ethylhexyl methoxycinnamate, 4% of cetyl PEG, 0.5% of NaOH, 0.5% of orange pigment and the balance of deionized water;
wherein, the salidroside nano-particles are prepared by the following method: 75mg of salidroside monomer powder is fully dissolved in 25mL of deionized water, 300uL of horseradish peroxidase solution (10 mg/mL) is added, an ultrasonic probe is immersed in the reaction solution after uniform stirring, the probe is adjusted to a working state (400W, 40 kHz), ultrasonic treatment is carried out on the reaction solution, the reaction solution is operated in a pulse mode of 1.6s on/0.4 s off, a water bath device is additionally added to maintain the reaction system at 45 ℃, after 4h ultrasonic treatment, the reaction system is gradually changed from colorless and transparent to turbid, the obtained solution is rapidly subjected to centrifugal treatment (15000 r/min,8 min), and the obtained precipitate is washed three times by the deionized water, so as to obtain the salidroside nanoparticle.
The agent B consists of the following components in percentage by mass: hydrogen peroxide 20%, oleyl alcohol 15%, oleic acid 12%, propylene glycol 12%, isopropyl alcohol 15%, sodium dodecyl sulfonate 2%, hydrated silica 1%, phosphoric acid to adjust pH to 3, and the balance deionized water.
The preparation method of the hair dye containing the salidroside nano-particles comprises the following steps:
s1, preparing an A agent
S101, mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 ℃ to obtain a water phase;
s102, mixing and heating isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG to 60 ℃ to obtain an oil phase;
s103, adding the oil phase into the water phase, stirring, preserving heat at 60 ℃ for 10min, then adding 5, 6-dihydroxyindole, salidroside nanoparticles and orange pigment, stirring for 5min, and regulating the pH value by using NaOH to prepare an agent A;
s2, preparation of agent B
S201, mixing deionized water, propylene glycol, sodium dodecyl sulfonate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
s202, mixing oleyl alcohol, oleic acid and isopropanol, and heating to 60 ℃ to obtain an oil phase;
s203, adding the oil phase into the water phase, stirring, preserving heat at 60 ℃ for 10min, then adding hydrogen peroxide, and regulating the pH to 3 by using phosphoric acid to prepare the agent B.
Example 4:
a hair dye containing salidroside nanoparticles, comprising: agent A and agent B;
the agent A consists of the following components in percentage by mass: 5, 6-dihydroxyindole 5%, salidroside nanoparticle 2%, isohexadecane 3%, PPG-14 butyl ether 3%, oleic acid 8%, glycerol 12%, butanediol 12%, sodium sulfite 6%, ethylhexyl methoxycinnamate 8%, cetyl PEG 6%, naOH 1%, orange pigment 1%, and deionized water in balance;
wherein, the salidroside nano-particles are prepared by the following method: 75mg of salidroside monomer powder is fully dissolved in 25mL of deionized water, 300uL of horseradish peroxidase solution (10 mg/mL) is added, an ultrasonic probe is immersed in the reaction solution after uniform stirring, the probe is adjusted to a working state (400W, 40 kHz), ultrasonic treatment is carried out on the reaction solution, the reaction solution is operated in a pulse mode of 1.6s on/0.4 s off, a water bath device is additionally added to maintain the reaction system at 45 ℃, after 4h ultrasonic treatment, the reaction system is gradually changed from colorless and transparent to turbid, the obtained solution is rapidly subjected to centrifugal treatment (15000 r/min,8 min), and the obtained precipitate is washed three times by the deionized water, so as to obtain the salidroside nanoparticle.
The agent B consists of the following components in percentage by mass: 26% of hydrogen peroxide, 18% of oleyl alcohol, 15% of oleic acid, 15% of propylene glycol, 18% of isopropanol, 2% of sodium dodecyl sulfonate, 2% of hydrated silica, and the balance of deionized water.
The preparation method of the hair dye containing the salidroside nano-particles comprises the following steps:
s1, preparing an A agent
S101, mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 ℃ to obtain a water phase;
s102, mixing and heating isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG to 60 ℃ to obtain an oil phase;
s103, adding the oil phase into the water phase, stirring, preserving heat at 60 ℃ for 20min, then adding 5, 6-dihydroxyindole, salidroside nanoparticles and orange pigment, stirring for 10min, and regulating the pH value by using NaOH to prepare an agent A;
s2, preparation of agent B
S201, mixing deionized water, propylene glycol, sodium dodecyl sulfonate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
s202, mixing oleyl alcohol, oleic acid and isopropanol, and heating to 60 ℃ to obtain an oil phase;
s203, adding the oil phase into the water phase, stirring, preserving heat at 60 ℃ for 20min, then adding hydrogen peroxide, and regulating the pH to 3 by using phosphoric acid to prepare the agent B.
Example 5:
a hair dye containing salidroside nanoparticles, comprising: agent A and agent B;
the agent A consists of the following components in percentage by mass: 5, 6-dihydroxyindole 5%, salidroside nanoparticle 2%, isohexadecane 3%, PPG-14 butyl ether 3%, oleic acid 6%, glycerol 12%, butanediol 12%, sodium sulfite 4%, ethylhexyl methoxycinnamate 8%, cetyl PEG 6%, naOH0.5%, orange 0.5%, and deionized water in balance;
wherein, the salidroside nano-particles are prepared by the following method: 75mg of salidroside monomer powder is fully dissolved in 25mL of deionized water, 300uL of horseradish peroxidase solution (10 mg/mL) is added, an ultrasonic probe is immersed in the reaction solution after uniform stirring, the probe is adjusted to a working state (400W, 40 kHz), ultrasonic treatment is carried out on the reaction solution, the reaction solution is operated in a pulse mode of 1.6s on/0.4 s off, a water bath device is additionally added to maintain the reaction system at 45 ℃, after 4h ultrasonic treatment, the reaction system is gradually changed from colorless and transparent to turbid, the obtained solution is rapidly subjected to centrifugal treatment (15000 r/min,8 min), the obtained precipitate is washed three times by the deionized water, and the salidroside nanoparticle with the particle size of 312+/-93 nm is prepared, and an electron microscope image is shown in figure 1.
The agent B consists of the following components in percentage by mass: hydrogen peroxide 20%, oleyl alcohol 18%, oleic acid 12%, propylene glycol 12%, isopropyl alcohol 18%, sodium dodecyl sulfonate 3%, hydrated silica 1%, phosphoric acid to adjust the pH to 3, and the balance deionized water.
The preparation method of the hair dye containing the salidroside nano-particles comprises the following steps:
s1, preparing an A agent
S101, mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 ℃ to obtain a water phase;
s102, mixing and heating isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG to 60 ℃ to obtain an oil phase;
s103, adding the oil phase into the water phase, stirring, preserving heat at 60 ℃ for 20min, then adding 5, 6-dihydroxyindole, salidroside nanoparticles and orange pigment, stirring for 10min, and regulating the pH value by using NaOH to prepare an agent A;
s2, preparation of agent B
S201, mixing deionized water, propylene glycol, sodium dodecyl sulfonate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
s202, mixing oleyl alcohol, oleic acid and isopropanol, and heating to 60 ℃ to obtain an oil phase;
s203, adding the oil phase into the water phase, stirring, preserving heat at 60 ℃ for 20min, then adding hydrogen peroxide, and regulating the pH to 3 by using phosphoric acid to prepare the agent B.
Comparative example 1:
comparative example 1 differs from example 5 in that: the composition does not contain salidroside nanoparticles, and the rest is the same as in example 5.
Comparative example 2:
comparative example 2 differs from example 5 in that: the rhodiola rosea glycoside nanoparticles are not contained, the 5, 6-dihydroxyindole is replaced by p-phenylenediamine, and the rest is the same as in example 5.
Comparative example 3:
comparative example 3 differs from example 5 in that: the preparation process of the salidroside nano-particles does not have an ultrasonic step.
Test example:
1. white hair is taken and divided into 10 groups, each group is 2g, and hair dye in examples 1-5 and comparative examples 1-3 is used for carrying out smearing experiments on white hair samples, wherein the experimental process is as follows:
uniformly mixing the agent A and the agent B according to the mass ratio of 1:1, applying the mixture on hair, and cleaning the hair after 10min, wherein the test temperature is 28 ℃.
The above experimental results were scored according to the following criteria, and since the results of examples 1 to 4 are substantially the same as those of example 5, the hair dye effect of the hair dye is illustrated by taking the hair dye of example 5 as an example, and the specific results are shown in tables 1 and 2:
1-very bad; 2-worse; 3-general; 4-well; 5-very well.
TABLE 1 general results after dyeing of hair
Figure BDA0003189838840000131
Table 2 hair dyeing effect in 10 parallel experiments
Figure BDA0003189838840000132
In table 2, L, a, b are parameters of a standard international color space map, and the L value refers to black and white, and the larger the L value is, the whiter the L value is; the value a is red and green, and the larger the value a is, the more red is; the b value refers to yellow-blue, the greater the b value, the more yellow. As can be seen from Table 2, after fixation for 10 minutes, the values a and b in the present application are significantly higher than those of comparative examples 1, 2 and 3, compared with the primary color, and thus it can be seen that the hair dye provided by the present invention has good dyeing effect.
2. After washing the two hairdye of example 5 and comparative examples 1 to 3 10 times, the washing fastness test was carried out, the test method being referred to ISO 105-C01-C05-1989 "textile color fastness test washing fastness: test 1-test 5) and improvement, specifically: 2g of hair sample was placed in the hair dye, kneaded and fixed at 30℃for 10 minutes, mechanically stirred, rinsed, dried, and evaluated for color fastness to washing with a jetness instrument, and the test results are shown in Table 3.
TABLE 3 washing fastness test results
Figure BDA0003189838840000141
As is clear from Table 3, after the hair dye of the present invention is washed 10 times, the change of the a value and the b value is not obvious, and after the hair dye of the comparative examples 1 to 3 is washed 10 times, the a value and the b value are obviously reduced, which indicates that the hair dye provided by the present invention can be colored and fixed in a short time, and has good washing fastness and stable and durable effect.
1. Ultraviolet protection effect test
UVA, UVB and visible light may cause light loss to hair, the extent of loss varying with wavelength. UVB mainly causes loss of hair proteins and UVA promotes color changes. The ultraviolet protection of hair includes the protection of natural pigments of hair and the protection of external products, ultraviolet injury can be prevented by depositing hair dye on Mao Xiaopi and cortex, and the ultraviolet protection capability of different dyes is different. The invention adopts the same ultraviolet resistance test method as that of fabrics, samples are tested in a dry state and a loose state, 4 samples are tested, the samples do not need to be pre-conditioned, but special requirements on the test environment are required [ such as relative humidity (50% +/-20%) ]. Based on the ultraviolet transmittance obtained by the test, the average transmittance of UVA and UVB can be calculated for each wavelength, and T represents the ultraviolet transmittance, and the results are shown in table 4.
TABLE 4 UV protection effect
Figure BDA0003189838840000151
As shown in Table 4, the dye intermediate provided by the invention can effectively play a role in ultraviolet protection.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (8)

1. A hair dye containing salidroside nanoparticles, comprising: the dye comprises an agent A containing a dye and an agent B containing an oxidant, wherein the agent A contains 5, 6-dihydroxyindole and salidroside nanoparticles, and the weight ratio of the 5, 6-dihydroxyindole to the salidroside nanoparticles is 1-8:0.5-4;
the agent A consists of the following components in percentage by mass: 1-8% of 5, 6-dihydroxyindole, 0.5-4% of salidroside nano particles, 1-3% of isohexadecane, 1-3% of PPG-14 butyl ether, 6-12% of oleic acid, 6-12% of glycerol, 6-12% of butanediol, 4-8% of sodium sulfite, 4-8% of ethylhexyl methoxycinnamate, 2-6% of cetyl PEG, 0.5-4% of NaOH, 0.5-1% of orange pigment and the balance of deionized water;
the agent B consists of the following components in percentage by mass: 18-26% of hydrogen peroxide, 12-18% of oleyl alcohol, 12-18% of oleic acid, 12-18% of propylene glycol, 12-18% of isopropanol, 2-4% of sodium dodecyl sulfate, 1-2% of hydrated silica, adjusting the pH to 2.5-3.5 by phosphoric acid, and the balance of deionized water;
the salidroside nanoparticle is prepared by the following method: fully dissolving salidroside monomer powder in deionized water, adding horseradish peroxidase solution, stirring uniformly, performing ultrasonic treatment with ultrasonic frequency of 350-450W,35-45kHz, ultrasonic temperature of 40-50 ℃ and ultrasonic time of 3-5h, centrifuging after ultrasonic treatment, and washing.
2. The hair dye containing salidroside nanoparticles according to claim 1, wherein the agent A consists of the following components in percentage by mass: 1-5% of 5, 6-dihydroxyindole, 0.5-2% of salidroside nano particles, 1-3% of isohexadecane, 1-3% of PPG-14 butyl ether, 6-8% of oleic acid, 8-12% of glycerin, 8-12% of butanediol, 4-6% of sodium sulfite, 6-8% of ethylhexyl methoxycinnamate, 4-6% of cetyl PEG, 0.5-1% of NaOH, 0.5-1% of orange pigment and the balance of deionized water;
the agent B consists of the following components in percentage by mass: 20-26% of hydrogen peroxide, 15-18% of oleyl alcohol, 12-15% of oleic acid, 12-15% of propylene glycol, 15-18% of isopropanol, 2-4% of sodium dodecyl sulfate, 1-2% of hydrated silica, and the balance of deionized water, wherein the pH is adjusted to 2.5-3.5 by phosphoric acid.
3. The hair dye containing salidroside nanoparticles according to claim 2, wherein the agent A consists of the following components in percentage by mass: 5, 6-dihydroxyindole 5%, salidroside nanoparticle 2%, isohexadecane 3%, PPG-14 butyl ether 3%, oleic acid 6%, glycerol 12%, butanediol 12%, sodium sulfite 4%, ethylhexyl methoxycinnamate 8%, cetyl PEG 6%, naOH0.5%, orange 0.5%, and deionized water in balance;
the agent B consists of the following components in percentage by mass: hydrogen peroxide 20%, oleyl alcohol 18%, oleic acid 12%, propylene glycol 12%, isopropyl alcohol 18%, sodium dodecyl sulfonate 3%, hydrated silica 1%, phosphoric acid to adjust the pH to 3, and the balance deionized water.
4. The hair dye containing salidroside nanoparticles according to claim 1, wherein the weight ratio of salidroside monomer powder to horseradish peroxidase is 20-30:1.
5. The hair dye containing salidroside nanoparticles according to claim 1, wherein the ultrasonic frequency is 400w,40khz, the ultrasonic temperature is 45 ℃, and the ultrasonic time is 4 hours.
6. The method for preparing the hair dye containing the salidroside nanoparticles according to any one of claims 1 to 5, comprising the steps of:
s1, preparing an A agent
S101, mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 50-80 ℃ to obtain a water phase;
s102, mixing and heating isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG to 50-80 ℃ to obtain an oil phase;
s103, adding the oil phase into the water phase, stirring and preserving heat for 10-20min, then adding 5, 6-dihydroxyindole, salidroside nanoparticles and orange pigment, stirring for 5-10min, and regulating the pH value to 9-11 by using NaOH to prepare an agent A;
s2, preparation of agent B
S201, mixing deionized water, propylene glycol, sodium dodecyl sulfonate and hydrated silica, and heating to 50-80 ℃ to obtain a water phase;
s202, mixing oleyl alcohol, oleic acid and isopropanol, and heating to 50-80 ℃ to obtain an oil phase;
s203, adding the oil phase into the water phase, stirring and preserving heat for 10-20min, then adding hydrogen peroxide, and regulating the pH value to 2-4 by using phosphoric acid to prepare the agent B.
7. The method of using a hair dye containing salidroside nanoparticles according to any one of claims 1 to 5, comprising: mixing agent A and agent B at a mass ratio of 1-2:1-2, applying on hair, and cleaning hair after 8-12 min.
8. The application method according to claim 7, wherein the agent A and the agent B are uniformly mixed according to the mass ratio of 1:1, and the mixture is smeared on hair, and the hair is cleaned after 10 minutes.
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