A preparation method of hair dye and hair dye

Abstract

The present invention provides a preparation method of a hair dye and the hair dye, and relates to the technical field of daily chemical products. Specifically, graphene oxide is dispersed in a polar solvent, and a general structural formula (R 1 O)3SiR 2 R 3 R 4 CH3N + X ‑ The quaternary ammonium salt of the present invention is reacted for a certain time, filtered, washed and dried to obtain modified graphene oxide; the modified graphene oxide is dispersed in an amino silicone oil microemulsion, reacted for 30 min-24 hours, and the hair dye is obtained. The hair dye of the present invention has simple preparation steps, better dyeing effect, and longer dyeing duration.

Description

Technical Field

[0001] The invention belongs to the technical field of daily chemical products and relates to a preparation method of a hair dye and the hair dye. Background Art

[0002] As a new type of hair dye, graphene hair dye is highly environmentally friendly, does not damage hair quality, and can form a hair dyeing effect that gradually changes from yellow to black according to the concentration of graphene. The prior art discloses chemically combining graphene with amino silicone oil with quaternary ammonium salt so that it can be firmly combined with hair, but there are the following technical problems: (1) There are many reaction steps, usually up to 3-4 steps, which will result in a low yield; (2) The grafting efficiency of quaternary ammonium salt is low when quaternary ammonium salt is grafted onto amino silicone oil or grafted onto amino silicone oil by copolymerization, etc., resulting in insufficient hair dyeing effect. Summary of the invention

[0003] The purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a hair dye.

[0004] Another object of the present invention is to provide a hair dye.

[0005] The technical solution of the present invention is as follows:

[0006] A method for preparing a hair dye comprises the following steps:

[0007] S1. Dispersing graphene oxide in a polar organic solvent, adding a general structural formula (R 1 O)3SiR 2 R 3 R 4 CH3N + X - quaternary ammonium salt, react for a certain time, filter, wash, and dry to obtain modified graphene oxide; wherein R 1 is selected from C1-C6 alkyl or substituted alkyl, R 2 is selected from C1-C6 alkylene or substituted alkylene or aromatic or substituted aromatic groups, R 3 is selected from C12-C18 alkyl or substituted alkyl, R 4 An alkyl or substituted alkyl group selected from C1-C18;

[0008] S2. Dispersing the modified graphene oxide obtained in step S2 into the amino silicone oil microemulsion, reacting for 30 minutes to 24 hours, and obtaining the hair dye.

[0009] Preferably, the number of graphene oxide sheets in step S1 does not exceed 10.

[0010] Preferably, the weight ratio of graphene oxide, polar organic solvent and quaternary ammonium salt in step S1 is 1:(50-2000):(0.001-0.2).

[0011] Preferably, the weight concentration of the amino silicone oil microemulsion in step S2 is 10-70%.

[0012] Preferably, the weight ratio of the modified graphene oxide and the amino silicone oil microemulsion in step S2 is (0.05-0.3):(1-5).

[0013] Preferably, after the reaction in step S2 for 30 min to 24 hours, the following steps are further included:

[0014] Add reducing agent, raise the temperature to 60-80°C, and react for 0.5-24 hours.

[0015] More preferably, the reducing agent is selected from one or both of vitamin C and glucose.

[0016] More preferably, the weight ratio of the graphene oxide to the reducing agent is 1:(2-10)

[0017] Preferably, the reaction temperature in step S2 is room temperature to 80°C.

[0018] A hair dye is prepared by the preparation method described in any one of the above embodiments.

[0019] The graphene oxide surface has abundant active groups such as hydroxyl, carboxyl, epoxy group. The present invention first reacts the hydroxyl on the graphene oxide surface with the silicon-based alkoxy in the quaternary ammonium salt, and the quaternary ammonium salt is grafted to the surface of the graphene oxide to obtain quaternary ammonium salt modified graphene oxide. The quaternary ammonium salt modified graphene oxide is added to the commercially available aminosilicone oil microemulsion, and the amino on the aminosilicone oil in the aminosilicone oil microemulsion reacts with the active groups such as the carboxyl, epoxy group on the modified graphene oxide surface. Due to the hydrophobicity of the aminosilicone oil and the hydrophilicity of the modified graphene oxide, the reaction occurs at the interface of the microemulsion, and the graphene sheet and the microemulsion form a state of mutual blending at the interface of the microemulsion, and the structure is stable. Therefore, the hair dye of the present invention can load more proportions of graphene oxide (or graphene).

[0020] Different from the prior art method of first preparing amino silicone oil modified by quaternary ammonium salt, reacting with reactive graphene, and then dispersing in water to form a hair dye, the present invention first reacts commercially available quaternary ammonium salt containing alkoxysilane with graphene oxide to obtain quaternary ammonium salt modified graphene oxide, and then directly reacts with commercially available amino silicone oil microemulsion to obtain the hair dye. Therefore, the method of the present invention has fewer steps and is simpler.

[0021] The beneficial effects of the present invention are:

[0022] (1) The preparation steps of the present invention are simple and the cost is lower.

[0023] (2) The present invention combines the properties of graphene oxide (or graphene) sheets and microemulsions. The microemulsions provide good permeability and spreadability, thereby improving the deposition ability of graphene oxide (or graphene) on hair.

[0024] (3) The aminosilicone oil microemulsion of the present invention also has a good conditioning effect on hair quality.

[0025] (4) The electropositive property of the quaternary ammonium salt of the present invention improves the adsorption effect of graphene oxide (or graphene) on electronegative hair.

[0026] (5) The hair dye of the present invention has a better dyeing effect because it carries a larger proportion of graphene oxide (or graphene). It can be dyed with a smaller amount or at a lower concentration after dilution, and the dyeing lasts longer. DETAILED DESCRIPTION

[0027] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0028] The present invention provides a method for preparing a hair dye, comprising the following steps:

[0029] S1. Dispersing graphene oxide in a polar organic solvent, adding a general structural formula (R 1 O)3SiR 2 R 3 R 4 CH3N + X - quaternary ammonium salt, react for a certain time, filter, wash, and dry to obtain modified graphene oxide; wherein R 1 is selected from C1-C6 alkyl or substituted alkyl, R 2 is selected from C1-C6 alkylene or substituted alkylene or aromatic or substituted aromatic groups, R 3 is selected from C12-C18 alkyl or substituted alkyl, R 4 An alkyl or substituted alkyl group selected from C1-C18;

[0030] S2. Dispersing the modified graphene oxide obtained in step S2 into the amino silicone oil microemulsion, reacting for 30 minutes to 24 hours, and obtaining the hair dye.

[0031] There is no particular limitation on the polar organic solvent in step S1 of the present invention, as long as it can disperse graphene oxide and dissolve the quaternary ammonium salt. Specifically, it can be selected from anhydrous ethanol, acetone, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, methanol, etc., or a mixed solvent of these solvents, such as a mixed solvent of acetone and anhydrous ethanol, or a mixed solvent of anhydrous ethanol and butyl acetate.

[0032] The reaction time in step S1 of the present invention is 1-24 hours. The time varies according to the reaction temperature. The higher the reaction temperature, the shorter the time. For example, the reaction time at room temperature is 20-24 hours, and the reaction time at 60° C. can be 10-15 hours.

[0033] In a preferred embodiment, the number of graphene oxide sheets in step S1 is no more than 10. In a more preferred embodiment, the graphene oxide can be selected from Hummers graphene oxide or modified Hummers graphene oxide.

[0034] In a preferred embodiment, the quaternary ammonium salt can be specifically selected from one or more of trimethoxysilylpropyl octadecyldimethylammonium chloride, trimethoxysilylpropyl octadecyldimethylammonium bromide, triethoxysilylpropyl octadecyldimethylammonium chloride, triethoxysilylpropyl octadecyldimethylammonium bromide, trimethoxysilylpropyl octadecyloctylmethylammonium chloride and trimethoxysilylpropyl octadecyloctylmethylammonium bromide, trimethoxysilylpropyl octadecylmethylbenzylammonium chloride, triethoxysilylpropyl octadecylmethylbenzylammonium chloride, trimethoxysilylpropyl octadecylmethylbenzylammonium bromide and triethoxysilylpropyl octadecylmethylbenzylammonium bromide.

[0035] In a preferred embodiment, the weight ratio of graphene oxide, polar organic solvent and quaternary ammonium salt in step S1 is 1:(50-2000):(0.001-0.2). More preferably, the weight ratio is 1:(100-1000):(0.005-0.1). More specifically, the weight ratio of graphene oxide and quaternary ammonium salt can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09 or 1:0.1.

[0036] In a preferred embodiment, the weight concentration of the aminosilicone oil microemulsion in step S2 is 10-70%. More preferably, the weight concentration of the aminosilicone oil microemulsion is 30-70%, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%. The average particle size of the aminosilicone oil microemulsion in the present invention is not particularly limited, but it is more suitable to be 50-500μm, more preferably 100-300μm, such as 100μm, 120μm, 150μm, 180μm, 200μm, 220μm, 250μm, 280μm or 300μm.

[0037] In a preferred embodiment, the weight ratio of the modified graphene oxide and the amino silicone oil microemulsion in step S2 is (0.05-0.3):(1-5). More preferably, the weight ratio of the modified graphene oxide and the amino silicone oil microemulsion is (0.1-0.2):(1-3), such as 0.1:1, 0.1:1.5, 0.1:2, 0.1:2.5, 0.1:3, 0.15:1, 0.15:2, 0.15:2.5, 0.2:1, 0.2:1.5 or 0.2:2.5.

[0038] In a preferred embodiment, after reacting for 30 min to 24 hours in step S2, the following steps are further included:

[0039] Add a reducing agent, raise the temperature to 60-80°C, and react for 0.5-24 hours. More preferably, the reaction time is 1-10 hours.

[0040] In a more preferred embodiment, the reducing agent is selected from one or both of vitamin C and glucose.

[0041] In a more preferred embodiment, the weight ratio of graphene oxide to the reducing agent is 1:(2-10). More specifically, the weight ratio of graphene oxide to the reducing agent may be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0042] In a preferred embodiment, the reaction temperature in step S2 is from room temperature to 80°C.

[0043] The present invention also provides a hair dye prepared by the preparation method described in any of the above embodiments.

[0044] The technical solution of the present invention is further described and illustrated according to various embodiments below. Unless otherwise specified, the parts described in the following embodiments are parts by weight.

[0045] Example 1

[0046] Disperse 1 part of Hummers graphene oxide with a sheet thickness of no more than 5 layers in 300 parts of anhydrous ethanol, add 0.01 part of trimethoxysilylpropyl octadecyl dimethyl ammonium chloride, react at 50° C. for 8 hours, filter, wash with deionized water, and dry to obtain modified graphene oxide;

[0047] One part of the modified graphene oxide was dispersed in 10 parts of 40 wt % amino silicone oil microemulsion, the temperature was raised to 50° C., and the mixture was stirred for reaction for 5 hours to obtain a hair dye.

[0048] Example 2

[0049] Disperse 1 part of Hummers graphene oxide with a sheet thickness of no more than 5 layers in 1000 parts of anhydrous ethanol, add 0.02 parts of triethoxysilylpropyl octadecyl dimethyl ammonium chloride, react at 55° C. for 10 hours, filter, wash with deionized water, and dry to obtain modified graphene oxide;

[0050] Disperse 1 part of the modified graphene oxide into 15 parts of 50 wt% amino silicone oil microemulsion, heat to 50°C, react for 9 hours, add 8 parts of vitamin C, continue to react for 12 hours, and obtain a hair dye.

[0051] Example 3

[0052] Disperse 1 part of modified Hummers graphene oxide with a sheet thickness of no more than 5 layers in 500 parts of acetone, add 0.05 parts of trimethoxysilylpropyl octadecyl dimethyl ammonium chloride, react at 50° C. for 8 hours, filter, wash with anhydrous ethanol, and dry to obtain modified graphene oxide;

[0053] Disperse 1 part of the modified graphene oxide into 20 parts of 50 wt% amino silicone oil microemulsion, heat to 60°C, react for 6 hours, add 5 parts of vitamin C, continue to react for 10 hours, and obtain a hair dye.

[0054] Example 4

[0055] The hair dye was obtained by replacing 0.05 parts of trimethoxysilylpropyl octadecyl dimethyl ammonium chloride in Example 3 with 0.07 parts of trimethoxysilylpropyl octadecyl dimethyl ammonium chloride and keeping the other steps unchanged.

[0056] Example 5

[0057] The amino silicone oil microemulsion with a concentration of 50 wt % in Example 3 was replaced with an amino silicone oil microemulsion with a concentration of 70 wt % to obtain a hair dye.

[0058] Example 6

[0059] The hair dye was obtained by replacing 0.05 parts of trimethoxysilylpropyl octadecyl dimethyl ammonium chloride in Example 3 with 0.03 parts of trimethoxysilylpropyl octadecyl dimethyl ammonium chloride and keeping the other steps unchanged.

[0060] Example 7

[0061] The hair dye is obtained by replacing 20 parts of amino silicone oil microemulsion in Example 3 with 30 parts of amino silicone oil microemulsion and keeping the other steps unchanged.

[0062] Comparative Example 1

[0063] The amino silicone oil microemulsion in Example 3 was replaced with a milky amino silicone oil emulsion, and the other steps remained unchanged to obtain a hair dye.

[0064] Comparative Example 2

[0065] Add 100 parts of epoxy-modified silicone oil with a viscosity (25°C) of 2400mPa.s and an epoxy value of 0.08mol / 100g, 11.7 parts of diethylamine and 111 parts of anhydrous ethanol into a container, raise the temperature to 65°C to react for 5 hours, raise the temperature to 80°C and distill at normal pressure to remove the anhydrous ethanol, reduce the pressure to below -0.095MPa, and distill at 100°C to remove the unreacted raw materials to obtain a light yellow tertiary amine-modified silicone oil with a slight amine odor.

[0066] Add 50 parts of octamethylcyclotetrasiloxane, 20 parts of aminopropylmethyldiethoxysilane, 50 parts of tertiary amine modified silicone oil, 3 parts of 3mPa.s dimethyl silicone oil at 25°C and 1.2 parts of 1wt% ammonium gel in a container, heat to 110-120°C, react for 1.5 hours, then heat to 140°C, keep constant temperature for 0.5 hour, reduce the pressure to below -0.095MPa, remove low boiling points, and obtain light yellow transparent amino copolymer silicone oil with a slight amine odor.

[0067] Add 100 parts of amino copolymer silicone oil, 130 parts of anhydrous ethanol and 2.5-di-tert-butylhydroquinone into a container, raise the temperature to 65°C, add dropwise a mixture of 30 parts of chlorooctadecane and 1.5 parts of sodium iodide, continue the reaction for 36 hours after the addition is complete, filter out the antioxidant residue, raise the temperature to 140°C, reduce the pressure to below -0.099 MPa, evaporate the unreacted matter, and obtain a light yellow viscous amino-containing quaternary ammonium silicone oil.

[0068] One part of modified Hummers graphene oxide with a flake thickness of no more than 5 layers is added to 1000 parts of deionized water, and ultrasonicated at 60 kHz for 20 minutes at room temperature to obtain a graphene oxide dispersion, the temperature is raised to 90°C, and 10 parts of amino-containing quaternary ammonium silicone oil are added at a stirring speed of 250 rpm, and the reaction is continued for 20 hours to obtain a hair dye.

[0069] Comparative Example 3

[0070] In Comparative Example 2, 1 part of modified Hummers graphene oxide with a sheet thickness of no more than 5 layers was added to 20 parts of deionized water instead of 1000 parts of deionized water, and the other steps remained unchanged. It was found that the obtained hair dye had obvious yellow-black solids that were not evenly dispersed.

[0071] Comparative Example 4

[0072] In Comparative Example 2, after adding the amino-containing quaternary ammonium silicone oil and continuing the reaction for 20 hours, 5 parts of vitamin C were added and the reaction was continued for another 10 hours to obtain a hair dye.

[0073] Evaluation of storage stability of hair dye

[0074] The hair dyes of Examples 1 to 7 and Comparative Examples 1, 2 and 4 were placed at 40° C. for 30 days, 45 days, 60 days and 75 days respectively to observe whether precipitation occurred. The specific results are shown in Table 1.

[0075] Table 1 Comparison of hair dye stability over time

[0076]

[0077]

[0078] From the results in Table 1, it can be seen that the hair dye of the present invention still has good stability even at a higher concentration of graphene oxide (or graphene). Therefore, the hair dye of the present invention can be used after being diluted with water or can be used directly.

[0079] Hair Dyeing and Reviews

[0080] (1) Hair dyeing: The same weight of the hair dyes of Examples 1 to 7 and Comparative Examples 1, 2 and 4 were applied to the same weight of commercially available hair bundles, and the hair bundles were left at room temperature for 30 minutes. The hair bundles were then washed with a commercially available 2-in-1 shampoo and dried naturally to obtain four types of "just dyed" hair bundles.

[0081] The hair dye of Example 3 was diluted 10 times with purified water and then dyed according to the above-mentioned hair dyeing method.

[0082] (2) Evaluation of fading degree: The hair bundles "just after dyeing" were washed 20 times and 30 times with commercially available 2 and 1 shampoos respectively and then dried naturally, which were "washed 20 times" and "washed 30 times". The color difference of the hair bundles "washed 20 times", "washed 30 times" and "just after dyeing" was evaluated visually by 20 trained participants according to the following evaluation criteria, and the average of the remaining 18 scores after removing the highest and lowest values ​​was taken as the result. The results are shown in Table 2.

[0083] Five evaluation criteria for fading:

[0084] 5--There is almost no color difference between the color just after dyeing and after fading;

[0085] 4--The color difference between just dyed and faded is small;

[0086] 3--The color difference between just dyed and faded is moderate;

[0087] 2--The color difference is large after dyeing and after fading;

[0088] 1--The color difference between just dyeing and after fading is very large.

[0089] Table 2 Comparison of fading degree after washing of dyed hair

[0090] Hair dye Wash 20 times Wash 30 times Example 1 3.8 2.9 Example 2 3.6 2.8 Example 3 3.6 3.0 Example 3 - dilution 10 times 3.5 2.8 Example 4 3.8 3.1 Example 5 3.5 2.9 Example 6 3.6 2.7 Example 7 3.7 2.8 Comparative Example 1 3.1 1.2 Comparative Example 2 3.5 2.2 Comparative Example 4 3.4 2.4

[0091] Therefore, it can be seen from the data in Table 2 that the hair dye of the present invention has better dyeing stability and can last longer after dyeing. The inventor believes that the hair dye of the present invention has better dyeing stability and is related to the high effective concentration of the hair dye of the present invention. The high effective concentration of the hair dye means that the concentration of graphene oxide or graphene is high, and the high concentration of graphene oxide or graphene means that the content of quaternary ammonium salt is also high, which can have more electrostatic interaction with negatively charged hair and stronger adsorption force. In addition, the present invention uses amino silicone oil microemulsion, which has a small particle size and strong penetration, and can penetrate deeper into the hair and bind more firmly.

[0092] As described above, the basic principles, main features and advantages of the present invention are shown and described. Those skilled in the art should understand that the present invention is not limited by the above embodiments, which are only preferred embodiments of the present invention and cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the scope of the present invention and the content of the specification should still be within the scope of the present invention. The scope of protection required by the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing a hair dye, characterized in that: The following steps are included: S1. Dispersing graphene oxide in a polar organic solvent, adding a general structural formula (R 1 O)3SiR 2 R 3 R 4 CH3N + X - quaternary ammonium salt, react for a certain time, filter, wash, and dry to obtain modified graphene oxide; wherein R 1 is selected from C1-C6 alkyl or substituted alkyl or aromatic or substituted aromatic groups, R 2 is selected from C1-C6 alkylene or substituted alkylene, R 3 is selected from C12-C18 alkyl or substituted alkyl, R 4 is selected from C1-C18 alkyl or substituted alkyl, X - Cl - or Br - ; S2. Dispersing the modified graphene oxide obtained in step S1 into the amino silicone oil microemulsion, reacting for 30 minutes to 24 hours, and obtaining the hair dye.

2. According to the method for preparing a hair dye according to claim 1, the number of graphene oxide sheets in step S1 does not exceed 10.

3. The method for preparing a hair dye according to claim 1, wherein the weight ratio of the graphene oxide, the polar organic solvent and the quaternary ammonium salt in step S1 is 1:(50-2000):(0.001-0.2).

4. The method for preparing a hair dye according to claim 1, wherein the weight concentration of the amino silicone oil microemulsion in step S2 is 10-70%.

5. The method for preparing a hair dye according to claim 1, wherein the weight ratio of the modified graphene oxide to the aminosilicone oil microemulsion in step S2 is (0.1-0.2):(1-3).

6. The method for preparing a hair dye according to claim 1, wherein after the reaction in step S2 is carried out for 30 minutes to 24 hours, the method further comprises the following steps: Add reducing agent, raise the temperature to 60-80°C, and react for 0.5-24 hours.

7. The method for preparing a hair dye according to claim 6, wherein the reducing agent is selected from one or both of vitamin C and glucose.

8. The method for preparing a hair dye according to claim 6, wherein the weight ratio of the graphene oxide to the reducing agent is 1:(2-10).

9. The method for preparing a hair dye according to claim 1, wherein the reaction temperature in step S2 is from room temperature to 80°C.

10. A hair dye, characterized in that: The method is prepared according to any one of claims 1 to 9.

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