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CN113520913B - Hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid - Google Patents

Hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid Download PDF

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Publication number
CN113520913B
CN113520913B CN202110874895.1A CN202110874895A CN113520913B CN 113520913 B CN113520913 B CN 113520913B CN 202110874895 A CN202110874895 A CN 202110874895A CN 113520913 B CN113520913 B CN 113520913B
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carboxylic acid
dihydroxyindole
hair dye
dihydroxyindole carboxylic
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CN113520913A (en
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李昊天
郭万才
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Chengdu Fuxin 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
    • A61K8/72Cosmetics 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
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/22Peroxides; Oxygen; Ozone
    • 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
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/23Sulfur; Selenium; Tellurium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25Silicon; Compounds thereof
    • 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
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • 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
    • 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
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    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes
    • A61K2800/432Direct dyes
    • A61K2800/4324Direct dyes in preparations 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
    • A61K2800/56Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
    • 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

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Abstract

The invention discloses a hair dye containing silicon dioxide nano particles loaded with dihydroxyindole carboxylic acid, which comprises an agent A and an agent B; the agent A comprises silica nano particles loaded with dihydroxyindole carboxylic acid, isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol, sodium sulfite, ethylhexyl methoxycinnamate, cetyl PEG and orange pigment; the agent B comprises hydrogen peroxide, oleyl alcohol, oleic acid, propylene glycol, isopropanol, sodium dodecyl sulfate and hydrated silica. The hair dye disclosed by the invention has a good dyeing effect, can still keep a good dyeing effect after being washed by water for many times, has excellent uvioresistant performance, and can effectively solve the technical problem of poor dyeing effect of the existing hair dye.

Description

Hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid
Technical Field
The invention relates to a hair dye, and in particular relates to a hair dye containing silicon dioxide nano particles loaded with dihydroxyindole carboxylic acid.
Background
In the present society, hair dyeing is very common in the elderly, middle-aged and young as an image changing mode, and hair dyes and other hair dyeing products adopted in the hair dyeing process are increasingly popular. Most of hair dyes adopted in the current market are aniline materials, and the hair dyes are toxic and have abnormal odor, so that the hair dyes can cause cancer. Melanin is a biological pigment, which is found in the body of everyone, and is formed from tyrosine or 3, 4-dihydroxyphenylalanine through a series of chemical reactions. It is the presence of melanin that the skin and hair have color. Dopa is the precursor of melanin, and is oxidized by tyrosine to release melanin. The partial oxidation product of dopamine, dihydroxyindole carboxylic acid, is similar to 5, 6-dihydroxyindole but is less susceptible to oxidation than is the case with 5, 6-dihydroxyindole. Because the compound is a substance produced by organisms, the compound has excellent biocompatibility, no toxicity and side effects, is an important intermediate for synthesizing melanin, and is used for replacing aniline and phenol compounds in some washing and chemical products at present.
In the existing artificial melanin hair dye, the partial oxidation product 5, 6-dihydroxyindole of dopamine has extremely high activity, three reaction sites exist, and the partial oxidation product can be oxidized into indoloquinone in air for a short time, so that the partial oxidation product is particularly easy to be oxidized excessively to lose efficacy in application. The disappearance of the hydroxyl active sites weakens the bonding force between the hydroxyl active sites and the micromolecular pigments, which can result in the reduction of the colorful hair dyeing effect, and no method is available for coloring the micromolecular inside the hair, so that the micromolecular is particularly easy to wash off and cannot be used for a long time, the colorful hair dyeing effect is influenced, and the practical application of the hair dye is greatly influenced. In addition, a large amount of reducing agent is required to be additionally added during storage, and the addition is contradictory to the oxidative polymerization of indole, so that the process is complex, the operation is troublesome, and the hair dyeing effect is seriously influenced.
Disclosure of Invention
Aiming at the prior art, the invention provides a hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid, which aims to solve the technical problem of poor hair dyeing effect of the existing hair dye.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: provided is a hair dye containing silica nanoparticles carrying dihydroxyindole carboxylic acid, which is characterized by comprising an agent A and an agent B; the agent A comprises the following components in percentage by mass:
2-14% of silica nano particles loaded with dihydroxyindole carboxylic acid, 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, 0.5-1% of orange pigment and the balance of deionized water;
the agent B comprises 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, 3% of sodium dodecyl sulfate, 1-2% of hydrated silica and the balance of deionized water;
the agent A and the agent B are stored separately and mixed according to the mass ratio of 1.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the agent A comprises the following components in percentage by mass:
2-14% of silica nano particles loaded with dihydroxyindole carboxylic acid, 1-3% of isohexadecane, 1-3% of PPG-14 butyl ether, 6-8% of oleic acid, 8-12% of glycerol, 8-12% of butanediol, 4-6% of sodium sulfite, 6-8% of ethylhexyl methoxycinnamate, 4-6% of cetyl PEG and 0.5% of orange pigment, and the balance of deionized water;
the agent B comprises 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, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
Further, the agent A comprises the following components in percentage by mass:
9% of silica nano particles loaded with dihydroxyindole carboxylic acid, 3% of isohexadecane, 3% of PPG-14 butyl ether, 7% of oleic acid, 11% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG and 0.5% of orange pigment, and the balance of deionized water;
the agent B comprises the following components in percentage by mass:
20% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
Further, the silica nanoparticle loaded with the dihydroxyindole carboxylic acid is prepared by the following steps:
s1: dissolving silicon dioxide nano particles and dihydroxyindole carboxylic acid in an organic solvent according to the mass ratio of 1-2, and performing ultrasonic pulse treatment at the temperature of 28-32 ℃ for 8-12 min to obtain a product solution;
s2: and (3) centrifuging the product solution, taking the precipitate, and washing the precipitate for 2-4 times by using the same organic solvent as the organic solvent in the S1 to obtain the product.
Further, the dihydroxyindole carboxylic acid is 5, 6-dihydroxyindole carboxylic acid (DHICA), and the organic solvent is methanol.
Further, the pulse pattern of the ultrasonic pulse treatment in S1 was 1.6S on/0.4S off.
Further, the agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 50-80 ℃ to obtain a water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 50-80 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, uniformly stirring, keeping the temperature at 50-80 ℃ for 10-20 min, adding the silica nanoparticles loaded with the dihydroxyindole carboxylic acid and the orange pigment, continuously stirring for 5-10 min, and adjusting the pH value to 9-11 to obtain the compound.
Further, the reagent used for pH adjustment in step (3) is sodium hydroxide.
Further, the agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 50-80 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol and heating to 50-80 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring uniformly, preserving heat for 10-20 min at 50-80 ℃, adding hydrogen peroxide, and adjusting the pH value to 2-4 to obtain the water-soluble organic fertilizer.
Further, the reagent used for pH adjustment in step (3) is phosphoric acid.
The invention has the beneficial effects that:
1. the ultrasonic synthesis method of the silica nanoparticles loading the dihydroxyindole carboxylic acid is originally created, the preparation method is quick and effective, and the method is suitable for large-scale use and preparation.
2. Dihydroxyindole carboxylic acid is another important component of melanin, and compared with 5, 6-dihydroxyindole, dihydroxyindole carboxylic acid has one more carboxyl group in structure than 5, 6-dihydroxyindole, so that the oxidation reaction site is reduced by one, and compared with the oxidation reaction site, the dihydroxyindole carboxylic acid is not easily oxidized in the air, but can be easily oxidized to black by adding a small amount of an oxidizing agent or changing the acid-base property of the system under specific conditions. Therefore, the hair dye has the advantages of 5, 6-dihydroxyindole, does not have the defect that the hair dye is easy to oxidize particularly, does not influence the binding force of the hair dye and small molecular pigment, and ensures the hair dyeing effect.
3. Because the silicon oxide nano particles have the properties of small particle size, good biocompatibility, easy entry into hair, easy attachment on the surface and inside of hair and the like, after the dihydroxyindole carboxylic acid is loaded on the silicon oxide nano particles, the dihydroxyindole carboxylic acid is easy to enter the hair, so that small molecules are colored inside the hair, the nanocrystallization of the small molecules gradually plays a role from inside to outside, the colored small molecules are not easy to wash off, and the dyeing effect can be maintained for a long time.
4. Dioxindole carboxylic acid has good ultraviolet resistance, and can enhance the ultraviolet resistance of hair by being introduced into the hair dye.
Drawings
FIG. 1 is a graph showing ultraviolet absorption spectra of the hair dyes of example 1 and comparative example 1.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
Example 1
A hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid comprises an agent A and an agent B; the agent A comprises the following components in percentage by mass:
9% of 5, 6-dihydroxyindole carboxylic acid-loaded silica nanoparticles, 3% of isohexadecane, 3% of PPG-14 butyl ether, 7% of oleic acid, 11% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG, 0.5% of orange pigment and the balance of deionized water.
The silicon dioxide nano particles loaded with 5, 6-dihydroxyindole carboxylic acid in the agent A are prepared by the following steps:
s1: dissolving silicon dioxide nanoparticles and 5, 6-dihydroxyindole carboxylic acid in methanol according to the mass ratio of 1; the pulse mode of the ultrasonic pulse treatment is 1.6s on/0.4 s off;
s2: centrifuging the product solution at 16000rpm for 6min, collecting precipitate, and washing with methanol for 3 times.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 60 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring well, keeping the temperature at 60 ℃ for 15min, adding the silica nanoparticles loaded with 5, 6-dihydroxyindole carboxylic acid and the orange pigment, continuing stirring for 8min, adding a proper amount of sodium hydroxide, and adjusting the pH value to about 10 to obtain the product.
The agent B comprises the following components in percentage by mass:
20% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 60 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, keeping the temperature at 60 deg.C for 15min, adding hydrogen peroxide, adding appropriate amount of phosphoric acid, and adjusting pH to 3.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Example 2
A hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid comprises an agent A and an agent B; the agent A comprises the following components in percentage by mass:
2% of silica nano particles loaded with 5, 6-dihydroxyindole carboxylic acid, 3% of isohexadecane, 1% of PPG-14 butyl ether, 8% of oleic acid, 8% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 4% of cetyl PEG and 0.5% of orange pigment, and the balance being deionized water.
The silicon dioxide nano particles loaded with 5, 6-dihydroxyindole carboxylic acid in the agent A are prepared by the following steps:
s1: dissolving silicon dioxide nano particles and 5, 6-dihydroxyindole carboxylic acid in methanol according to the mass ratio of 1; the pulse mode of ultrasonic pulse treatment is 1.6s on/0.4 s off;
s2: centrifuging the product solution at 16000rpm for 6min, collecting precipitate, and washing with methanol for 2 times.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 50 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 50 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring well, keeping the temperature at 50 ℃ for 20min, adding the silica nanoparticles loaded with 5, 6-dihydroxyindole carboxylic acid and the orange pigment, continuing stirring for 5min, adding a proper amount of sodium hydroxide, and adjusting the pH value to about 11 to obtain the product.
The agent B comprises the following components in percentage by mass:
20% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 15% of propylene glycol, 15% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 80 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 80 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, keeping the temperature at 80 deg.C for 10min, adding appropriate amount of phosphoric acid, adding hydrogen peroxide, and adjusting pH to 3.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Example 3
A hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid comprises an agent A and an agent B; the agent A comprises the following components in percentage by mass:
14% of 5, 6-dihydroxyindole carboxylic acid-loaded silicon dioxide nanoparticles, 1% of isohexadecane, 3% of PPG-14 butyl ether, 6% of oleic acid, 12% of glycerol, 8% of butanediol, 6% of sodium sulfite, 6% of ethylhexyl methoxycinnamate, 6% of cetyl PEG, 0.5% of orange pigment and the balance of deionized water.
The silicon dioxide nano particles loaded with 5, 6-dihydroxyindole carboxylic acid in the agent A are prepared by the following steps:
s1: dissolving silicon dioxide nanoparticles and 5, 6-dihydroxyindole carboxylic acid in methanol according to the mass ratio of 1; the pulse mode of the ultrasonic pulse treatment is 1.6s on/0.4 s off;
s2: centrifuging the product solution at 16000rpm for 6min, collecting precipitate, and washing with methanol for 4 times.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 80 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 80 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring well, keeping the temperature at 80 ℃ for 10min, adding the silica nanoparticles loaded with 5, 6-dihydroxyindole carboxylic acid and the orange pigment, continuing stirring for 5min, adding a proper amount of sodium hydroxide, and adjusting the pH value to about 9 to obtain the product.
The agent B comprises the following components in percentage by mass:
26% of hydrogen peroxide, 15% of oleyl alcohol, 15% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 50 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 50 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, maintaining at 50 deg.C for 20min, adding hydrogen peroxide, adding appropriate amount of phosphoric acid, and adjusting pH to 4.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Example 4
A hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid comprises an agent A and an agent B; the agent A comprises the following components in percentage by mass:
2% of silica nanoparticles loaded with 5, 6-dihydroxyindole carboxylic acid, 3% of isohexadecane, 1% of PPG-14 butyl ether, 12% of oleic acid, 6% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG, 0.5% of orange pigment and the balance of deionized water.
The silicon dioxide nano particles loaded with 5, 6-dihydroxyindole carboxylic acid in the agent A are prepared by the following steps:
s1: dissolving silicon dioxide nanoparticles and 5, 6-dihydroxyindole carboxylic acid in methanol according to the mass ratio of 1; the pulse mode of ultrasonic pulse treatment is 1.6s on/0.4 s off;
s2: centrifuging the product solution at 16000rpm for 6min, collecting precipitate, and washing with methanol for 3 times.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 70 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 70 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring uniformly, keeping the temperature at 70 ℃ for 15min, adding the silica nanoparticles loaded with 5, 6-dihydroxyindole carboxylic acid and the orange pigment, continuing stirring for 8min, adding a proper amount of sodium hydroxide, and adjusting the pH value to about 10 to obtain the product.
The agent B comprises the following components in percentage by mass:
18% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 18% of propylene glycol, 12% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 70 deg.C to obtain water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 70 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, maintaining at 70 deg.C for 15min, adding hydrogen peroxide, adding appropriate amount of phosphoric acid, and adjusting pH to about 3.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Example 5
A hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid comprises an agent A and an agent B; the agent A comprises the following components in percentage by mass:
14% of 5, 6-dihydroxyindole carboxylic acid-loaded silicon dioxide nanoparticles, 1% of isohexadecane, 3% of PPG-14 butyl ether, 6% of oleic acid, 12% of glycerol, 6% of butanediol, 8% of sodium sulfite, 4% of ethylhexyl methoxycinnamate, 2% of cetyl PEG, 1% of orange pigment and the balance of deionized water.
The silicon dioxide nano particles loaded with 5, 6-dihydroxyindole carboxylic acid in the agent A are prepared by the following steps:
s1: dissolving silicon dioxide nanoparticles and 5, 6-dihydroxyindole carboxylic acid in methanol according to the mass ratio of 1; the pulse mode of ultrasonic pulse treatment is 1.6s on/0.4 s off;
s2: centrifuging the product solution at 16000rpm for 6min, collecting precipitate, and washing with methanol for 3 times.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 60 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring well, keeping the temperature at 60 ℃ for 20min, adding the silica nanoparticles loaded with 5, 6-dihydroxyindole carboxylic acid and the orange pigment, continuing stirring for 5min, adding a proper amount of sodium hydroxide, and adjusting the pH value to about 10 to obtain the product.
The agent B comprises the following components in percentage by mass:
26% of hydrogen peroxide, 12% of oleyl alcohol, 18% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 2% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 60 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, keeping the temperature at 60 deg.C for 10min, adding hydrogen peroxide, adding appropriate amount of phosphoric acid, and adjusting pH to about 3.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Comparative example 1
A hair dye containing dihydroxyindole carboxylic acid comprises agent A and agent B; the agent A comprises the following components in percentage by mass:
9% of 5, 6-dihydroxyindole carboxylic acid, 3% of isohexadecane, 3% of PPG-14 butyl ether, 7% of oleic acid, 11% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG, 0.5% of orange pigment and the balance of deionized water.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 60 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring well, keeping the temperature at 60 ℃ for 15min, adding 5, 6-dihydroxyindole carboxylic acid and orange pigment, stirring for 8min, adding a proper amount of sodium hydroxide, and adjusting the pH value to about 10 to obtain the final product.
The agent B comprises the following components in percentage by mass:
20% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 60 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, maintaining at 60 deg.C for 15min, adding hydrogen peroxide, adding appropriate amount of phosphoric acid, and adjusting pH to 3.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Comparative example 2
A hair dye containing silica nanoparticles loaded with dihydroxyindole comprises an agent A and an agent B; the agent A comprises the following components in percentage by mass:
9% of 5, 6-dihydroxyindole-loaded silica nanoparticles, 3% of isohexadecane, 3% of PPG-14 butyl ether, 7% of oleic acid, 11% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG and 0.5% of orange pigment, and the balance of deionized water.
The silicon dioxide nano particles loaded with 5, 6-dihydroxyindole in the agent A are prepared by the following steps:
s1: dissolving silicon dioxide nanoparticles and 5, 6-dihydroxyindole in methanol according to the mass ratio of 1; the pulse mode of ultrasonic pulse treatment is 1.6s on/0.4 s off;
s2: centrifuging the product solution at 16000rpm for 6min, collecting precipitate, and washing with methanol for 3 times.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 60 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring well, keeping the temperature at 60 ℃ for 15min, adding the silica nanoparticles loaded with 5, 6-dihydroxyindole and the orange pigment, continuing stirring for 8min, adding a proper amount of sodium hydroxide, and adjusting the pH value to about 10 to obtain the final product.
The agent B comprises the following components in percentage by mass:
20% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 60 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, maintaining at 60 deg.C for 15min, adding hydrogen peroxide, adding appropriate amount of phosphoric acid, and adjusting pH to 3.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Comparative example 3
A hair dye containing 5, 6-dihydroxyindole comprises agent A and agent B; the agent A comprises the following components in percentage by mass:
9% of 5, 6-dihydroxyindole, 3% of isohexadecane, 3% of PPG-14 butyl ether, 7% of oleic acid, 11% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG, 0.5% of orange pigment and the balance of deionized water.
The agent A is prepared by the following steps:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 60 deg.C to obtain water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 60 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, stirring, keeping the temperature at 60 deg.C for 15min, adding 5, 6-dihydroxyindole and orange pigment, stirring for 8min, adding appropriate amount of sodium hydroxide, and adjusting pH to about 10.
The agent B comprises the following components in percentage by mass:
20% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
The agent B is prepared by the following steps:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 60 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 60 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring, maintaining at 60 deg.C for 15min, adding hydrogen peroxide, adding appropriate amount of phosphoric acid, and adjusting pH to 3.
After the agent A and the agent B are prepared, the agent A and the agent B are stored separately, and are mixed according to the mass ratio of 1.
Analysis of results
The hair dye of example 1 was used as an example to explain the dyeing effect of the hair dye in the example 1, since the results of examples 2 to 5 were substantially the same as those of example 1, when white hair was used and the sample white hair was subjected to the smearing test using the hair dye of example and comparative example, respectively. The hair dyeing effect was evaluated as a score, with the following criteria:
a very poor 1; poor 2; generally 3; good 4; very well 5.
The dyeing effects of the hair dyes in examples and comparative examples are shown in Table 1.
TABLE 1 Hair dyeing Effect of Hair dyes
Figure BDA0003189998350000151
In order to verify the effect of the hair dye of the present invention, hair dyeing was performed by taking the hair dye prepared in example 1 as an example. The agent A and the agent B in the example 1 are mixed according to the mass ratio of 1. After 10min, the hair was washed and the hair dyeing effect was measured at 28 ℃ and the results are shown in Table 2. As can be seen from Table 2, the hair dyeing effect of the present invention is superior.
TABLE 2 Hair dyeing Effect of the Hair dye of example 1
Figure BDA0003189998350000161
Note: l, a and b are parameters of a standard international color space diagram, the value of L refers to black and white, and the larger the value of L is, the whiter the value of L is; the value a refers to red and green, and the larger the value a is, the redder the value a is; the b value means yellow blue, the larger the b value, the more yellow.
In order to verify the fixation effect of the hair dye, the hair dye prepared in example 1 was taken as an example and compared with the hair dye in the comparative example, and the results are shown in table 3.
TABLE 3 comparison of fixation effects of hair dyes
Figure BDA0003189998350000162
As can be seen from Table 3, the coloring agent of the present invention has good dyeing effect and strong color fixing ability, and can maintain good dyeing effect even after being washed for many times.
Compared with the example 1, the dihydroxyindole carboxylic acid is not loaded on the silica nanoparticles, and although the silica nanoparticles can bring better hair dyeing effect during hair dyeing, the dihydroxyindole carboxylic acid has poor biocompatibility, the hair dye can only be attached to the surface layer of hair, is easy to elute by water, and has poor color fixing effect.
Compared with the example 1, the dihydroxyindole carboxylic acid, instead of the dihydroxyindole carboxylic acid, supported on the silica nanoparticles can easily enter the hair under the action of the silica nanoparticles, but the dihydroxyindole is easily oxidized, so that the bonding force between the dihydroxyindole and the small molecular pigment is weakened, the colorful hair dyeing effect is reduced, and no way is provided for coloring the small molecules in the hair, so that the small molecules are particularly easy to wash off and cannot be used for a long time, and the colorful hair dyeing effect is influenced.
Compared with the comparative example 2, the dihydroxyindole is not loaded on the silica nanoparticles, and the color fixing effect is further deteriorated, which shows that the silica nanoparticles have an enhancement effect on the color fixing effect.
UVA, UVB and visible light may cause photodamage to hair, the extent of damage varying with wavelength. UVB mainly causes the loss of hair proteins, UVA promotes color change. The ultraviolet protection of hair includes the protection of natural pigments of hair itself and the protection of external products, and can prevent ultraviolet damage by depositing hair dyes on the hair cortex and the cortex, and the ultraviolet protection ability of different dyes is different. It is known from the analysis of the ultraviolet absorption spectra of the hairdye in test example 1 and comparative example 1 that the position of the absorption peak of dihydroxyindole carboxylic acid after being loaded is not changed between 280 and 380, as shown in fig. 1, which corresponds to UVB, and functions to perfectly absorb ultraviolet rays.
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited by the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.

Claims (8)

1. A hair dye containing silica nanoparticles carrying dihydroxyindole carboxylic acid is characterized by comprising an agent A and an agent B; the agent A comprises the following components in percentage by mass:
2-14% of silica nano particles loaded with dihydroxyindole carboxylic acid, 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, 0.5-1% of orange pigment and the balance of deionized water; the silica nanoparticle loaded with the dihydroxyindole carboxylic acid is prepared by the following steps:
s1: dissolving silicon dioxide nano particles and dihydroxyindole carboxylic acid in an organic solvent according to the mass ratio of 1-2, and performing ultrasonic pulse treatment at the temperature of 28-32 ℃ for 8-12 min to obtain a product solution; the dihydroxyindole carboxylic acid is 5, 6-dihydroxyindole carboxylic acid, and the organic solvent is methanol;
s2: centrifuging the product solution, taking the precipitate, and washing the precipitate for 2 to 4 times by using the same organic solvent as the organic solvent in the S1 to obtain the product;
the agent B comprises the following components in percentage by mass:
18 to 26 percent of hydrogen peroxide, 12 to 18 percent of oleyl alcohol, 12 to 18 percent of oleic acid, 12 to 18 percent of propylene glycol, 12 to 18 percent of isopropanol, 3 percent of sodium dodecyl sulfate, 1 to 2 percent of hydrated silica and the balance of deionized water;
the agent A and the agent B are stored separately and are mixed according to the mass ratio of 1.
2. The hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid according to claim 1, wherein the agent A consists of the following components in percentage by mass:
2-14% of silica nano particles loaded with dihydroxyindole carboxylic acid, 1-3% of isohexadecane, 1-3% of PPG-14 butyl ether, 6-8% of oleic acid, 8-12% of glycerol, 8-12% of butanediol, 4-6% of sodium sulfite, 6-8% of ethylhexyl methoxycinnamate, 4-6% of cetyl PEG and 0.5% of orange pigment, and the balance of deionized water;
the agent B comprises 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, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
3. The hair dye containing silica nanoparticles loaded with dihydroxyindole carboxylic acid according to claim 2, wherein the agent A consists of the following components in percentage by mass:
9% of silica nano particles loaded with dihydroxyindole carboxylic acid, 3% of isohexadecane, 3% of PPG-14 butyl ether, 7% of oleic acid, 11% of glycerol, 12% of butanediol, 4% of sodium sulfite, 8% of ethylhexyl methoxycinnamate, 6% of cetyl PEG and 0.5% of orange pigment, and the balance of deionized water;
the agent B comprises the following components in percentage by mass:
20% of hydrogen peroxide, 18% of oleyl alcohol, 12% of oleic acid, 12% of propylene glycol, 18% of isopropanol, 3% of sodium dodecyl sulfate, 1% of hydrated silica and the balance of deionized water.
4. The hair dye containing silica nanoparticles-supported dihydroindoxyl carboxylic acid according to claim 1, wherein: the pulse mode of the ultrasonic pulse treatment in S1 was 1.6S on/0.4S off.
5. The hair dye containing silica nanoparticles carrying dihydroxyindole carboxylic acid according to any one of claims 1 to 3, wherein the agent A is prepared by:
(1) Mixing deionized water, sodium sulfite and ethylhexyl methoxycinnamate, and heating to 50-80 ℃ to obtain a water phase;
(2) Mixing isohexadecane, PPG-14 butyl ether, oleic acid, glycerol, butanediol and cetyl PEG, and heating to 50-80 deg.C to obtain oil phase;
(3) Adding the oil phase into the water phase, uniformly stirring, keeping the temperature at 50-80 ℃ for 10-20 min, adding the silica nanoparticles loaded with the dihydroxyindole carboxylic acid and the orange pigment, continuously stirring for 5-10 min, and adjusting the pH value to 9-11 to obtain the product.
6. The hair dye containing silica nanoparticles-supported dihydroxyindole carboxylic acid according to claim 5, characterized in that: and (4) in the step (3), a reagent used for pH adjustment is sodium hydroxide.
7. The hair dye containing silica nanoparticles supporting dihydroxyindole carboxylic acid according to any one of claims 1 to 3, wherein the agent B is prepared by:
(1) Mixing deionized water, propylene glycol, sodium dodecyl sulfate and hydrated silica, and heating to 50-80 ℃ to obtain a water phase;
(2) Mixing oleic acid, oleyl alcohol and isopropanol, and heating to 50-80 ℃ to obtain an oil phase;
(3) Adding the oil phase into the water phase, stirring uniformly, keeping the temperature at 50-80 ℃ for 10-20 min, adding hydrogen peroxide, and adjusting the pH value to 2-4 to obtain the product.
8. The hair dye containing silica nanoparticles-supported dihydroxyindole carboxylic acid according to claim 7, characterized in that: the reagent used for pH adjustment in step (3) is phosphoric acid.
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