CN111621029B - Modified aluminum-based MOF material, preparation method and application thereof in hair products - Google Patents

Modified aluminum-based MOF material, preparation method and application thereof in hair products Download PDF

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CN111621029B
CN111621029B CN202010477993.7A CN202010477993A CN111621029B CN 111621029 B CN111621029 B CN 111621029B CN 202010477993 A CN202010477993 A CN 202010477993A CN 111621029 B CN111621029 B CN 111621029B
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mof material
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scalp
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CN111621029A (en
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何嫦娥
李清
陈英燕
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Zhuhai Siyu Biotechnology Co ltd
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    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
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    • A61K8/00—Cosmetics or similar toiletry preparations
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    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
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Abstract

The invention provides a modified aluminum-based MOF material, a preparation method and application thereof in hair products. The method comprises the steps of uniformly mixing soluble aluminum salt, an organic ligand and an organic solvent to obtain a mixed solution; heating the mixed solution to 130-150 ℃, adding a zinc compound, reacting at a constant temperature for 5-12 h, and performing ultrasonic treatment in the period; after the reaction is finished, cooling to room temperature, and filtering to obtain a modified MOF material primary product; and washing, activating and drying the initial product of the modified aluminum-based MOF material to obtain the modified aluminum-based MOF material. The scalp and hair dry powder product containing the modified aluminum-based MOF material avoids the defects that starch or modified starch has poor oil adsorption capacity and is easy to remain on hair to cause hair tangling and collapse, and the experience feeling of the product is higher.

Description

Modified aluminum-based MOF material, preparation method and application thereof in hair products
Technical Field
The invention belongs to the technical field of daily cosmetics, and particularly relates to a modified aluminum-based MOF material, a preparation method and application thereof in hair products.
Background
Shampoo, also known as shampoo, cream shampoo or shampoo, is a hair washing product which is most widely used, and is mainly used for cleaning grease, sweat stain, cells peeled off from the scalp, foreign dust, microorganisms, residues of styling products, bad smell and the like which are secreted by a human body and attached to the scalp and hair, and keeping the scalp and the hair clean and beautiful. Most of the traditional shampoo is viscous liquid, the main component is surfactant, when in use, hair needs to be wetted with water, the hair needs to be rubbed after being smeared with the shampoo, and then foam generated by washing with a large amount of water is washed until the hair is cleaned. However, in some situations, for example, no water is available or it is desirable to avoid water contact (e.g., traditional customs in some regions of china suggest that a parturient should not contact water during the month), which limits the use of some people. At present, dry-cleaning shampoos are disclosed, the principle of which is mainly to use starch or starch modified substances of various plant sources to adsorb grease, and then remove dirt by physical means, for example, Chinese patent CN109512686A discloses a no-clean shampoo, which does not need to be cleaned by water, does not contain synthetic surfactants, and has the components meeting the requirements of industrial specifications. However, the current commercial no-clean dry powder products have the following defects: (1) the starch or modified starch has poor grease adsorption capacity and is easy to remain on the hair, so that the hair is tangled and collapsed; (2) the formula is generally free of conditioning, poor in antistatic ability and poor in experience feeling; (3) the general formula has poor antibacterial and dandruff removing capability and is easy to cause the problem of head itching.
The Metal-Organic Frameworks (MOFs) are inorganic-Organic composite materials, which are crystalline materials with periodic network structures formed by self-assembling polydentate Organic ligands containing oxygen or nitrogen atoms and inorganic Metal ions, and are hybrid coordination polymers combining the stability of inorganic substances and the various modifiability of Organic substances. The MOFs have the remarkable characteristics of ultrahigh porosity and huge internal specific surface area, and have potential excellent adsorption capacity. The aluminum-based MOFs material (Al-MOF) is one of MIL-68 series materials, is synthesized for the first time by Laval tin research group represented by French scientist Farrey, and has good water stability. The structural unit is MO4(OH)2Octahedral structural unit and organic terephthalic acid ligand are bridged to form a network structure through alternate and ordered arrangement of triangular and hexagonal pore canals with diameters of
Figure BDA0002516454750000021
And
Figure BDA0002516454750000022
the aluminum-based MOFs (Al-MOF) material prepared by a special process overcomes the defect of poor skeleton stability of most MOFs materials, and the Al-MOF material is mostly applied to the aspects of gas storage, catalysis, liquid phase adsorption and the like.
Patent CN201910928237.9 is an application of Al-MOF material in the preparation of hair and scalp cleansing products, which applies Al-MOF material in hair and scalp cleansing products, and finds that it has good application performance in oil control and dandruff removal and itching relief. However, the Al-MOF material contains graphene oxide, and the graphene oxide is expensive and not beneficial to market popularization; moreover, the Al-MOF material has single performance and cannot meet higher requirements of consumers.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a modified aluminum-based MOF material.
Another object of the present invention is to provide a modified aluminum-based MOF material obtained by the above preparation method.
It is a further object of the present invention to provide the use of the above-described modified aluminum-based MOF materials in hair products.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a modified aluminum-based MOF material comprises the following steps:
(1) uniformly mixing soluble aluminum salt, organic ligand and organic solvent to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 130-150 ℃, adding a zinc compound, reacting at a constant temperature for 5-12 h, and performing ultrasonic treatment in the period; after the reaction is finished, cooling to room temperature, and filtering to obtain a modified aluminum-based MOF material primary product;
(3) and (3) washing, activating and drying the modified aluminum-based MOF material primary product obtained in the step (2) to obtain the modified aluminum-based MOF material.
The soluble aluminum salt in the step (1) is preferably one or two of aluminum nitrate and aluminum chloride; more preferably anhydrous aluminum chloride.
The organic ligand in step (1) is preferably terephthalic acid.
The organic ligand and the soluble aluminum salt in the step (1) are preferably mixed according to the mol ratio of (1-2): 1, calculating the mixture ratio.
The organic solvent in step (1) is preferably N, N-dimethylformamide.
The organic solvent is used as a reaction medium and does not participate in the reaction; the dosage is based on the condition that the soluble aluminum salt, the organic ligand and the zinc compound can be fully dissolved or dispersed.
The mixing in step (1) is preferably carried out by stirring under ultrasonic conditions until the mixture is uniform.
The power of the ultrasonic wave is preferably 20-30 KHz; more preferably 25 KHz.
The rotating speed of the stirring is preferably 200-300 rpm; more preferably 250 rpm.
The temperature increase in step (2) is preferably achieved by a gradient temperature increase.
The gradient temperature rise speed is preferably 1-3 ℃/min; more preferably 2 deg.C/min.
The zinc compound in the step (2) is preferably at least one of zinc gluconate, zinc laurate, zinc myristate, zinc palmitate, zinc stearate, zinc ricinoleate, zinc glycinate, zinc carbonate hydroxide, zinc acetylmethionate, zinc aspartate, zinc salicylate, zinc undecylenate, zinc lactate, zinc glycinate, zinc PCA and zinc oxide whiskers; more preferably zinc oxide whiskers.
The addition amount of the zinc compound is preferably calculated according to the mass of 0.1-1.5% of the aluminum element of the zinc element; more preferably, the zinc element accounts for 0.1 to 1.0 percent of the mass of the aluminum element; most preferably 1.0% by mass of the element zinc relative to the element aluminum.
The ultrasonic treatment in the step (2) is preferably carried out for 4-6 min every 30 min; more preferably, sonication is performed for 5min every 30 min.
The frequency of the ultrasonic treatment in the step (2) is preferably 20-30 KHz; more preferably 25 KHz.
The room temperature is 0-40 ℃; preferably 20-30 ℃; more preferably 24 to 28 DEG C
The washing in the step (3) is preferably performed by sequentially washing with N, N-dimethylformamide, acetone and deionization; more preferably, the washing is performed 3 times using N, N-dimethylformamide, then 2 times using acetone, and then 3 times using deionized water.
The activation in the step (3) is heating activation.
The heating and activating conditions are preferably calcination for 4-6 h in a nitrogen atmosphere tubular furnace at 250-350 ℃; more preferably, the calcination is carried out in a 300 ℃ nitrogen atmosphere tube furnace for 5 hours.
The drying in the step (3) is freeze drying.
The freeze drying condition is preferably drying for 2-4 h at 8-12 Pa and-40-60 ℃; more preferably, the drying is carried out at-50 ℃ under 10Pa for 3 h.
A modified aluminum-based MOF material is prepared by the method; it has the characteristics of large specific surface area, large pore volume, strong antibacterial activity and the like.
The modified aluminum-based MOF material is dry powder, the purity is more than or equal to 99.0 percent, and the water content is less than or equal to 0.3 percent.
The modified aluminum-based MOF material has the following element indexes:
TABLE 1
Figure BDA0002516454750000031
The element indexes of the modified aluminum-based MOF material are preferably as follows:
TABLE 2
Figure BDA0002516454750000041
The specific surface area and pore volume of the modified aluminum-based MOF material described in table 3 are as follows:
SBET(m2/g) SInt(m2/g) VTotal(cm2/g) VMicro(cm2/g)
modified aluminum-based MOF materials 1300～1400 970～990 0.63～0.69 0.49～0.54
Use of a modified aluminium-based MOF material as described above in hair products.
The hair product comprises dry cleaning powder for scalp and hair and fluffy powder for hair.
The dry cleaning powder for the scalp and the hair comprises the following components in percentage by mass: 5.0-10.0% of polyhydric alcohol, 5.0-10.0% of modified aluminum-based MOF material, 5.0-10.0% of excipient, 0.5-5.0% of humectant, 0.5-5.0% of conditioner, 0.05-0.1% of pH regulator and 50.0-60.0% of propellant.
The scalp and hair dry cleaning powder also comprises one or two of essence and preservative.
The essence meets the requirements of technical specification 2015 edition of cosmetic safety.
The content of the essence in the scalp hair dry-cleaning powder meets related regulations, and is preferably 0.05-0.1% of the mass of the scalp hair dry-cleaning powder.
The preservative is preferably at least one of benzoic acid, sodium benzoate and potassium sorbate.
The content of the preservative in the scalp hair dry-cleaning powder meets relevant regulations, and is preferably 0.2-0.5% of the mass of the scalp hair dry-cleaning powder.
The scalp hair dry-cleaning powder also comprises water, and the balance is water; preferably 11.0 to 22.0 mass%.
The water is preferably deionized water.
The polyhydric alcohol is preferably at least one of propylene glycol, glycerol, sorbitol, xylitol, 1, 3-butanediol, caprylyl glycol, hexylene glycol and pentylene glycol.
The excipient is preferably at least one of silica silylate, silica dimethylsilylate, silica polydimethylsiloxane silylate, aluminum starch octenyl succinate, sodium starch octenyl succinate, hydrolyzed corn starch and octenyl succinate.
The humectant is preferably at least one of betaine, chitin, hydrolyzed chitin, hydroxypropyl chitosan, hydroxyethyl chitosan, myristoyl/PCA chitosan, carboxybutyl chitosan, carboxymethyl chitosan succinamide, chitosan PCA salt, chitosan mono succinamide, chitosan glycolate, and chitosan lactate.
The conditioning agent is preferably at least one of methoxy PEG/PPG-25/4 polydimethylsiloxane, methoxy PEG-/PPG-7/3 aminopropyl polydimethylsiloxane, methoxy amino-terminated polydimethylsiloxane/silsesquioxane copolymer and trimethoxysilyl polydimethylsiloxane.
The pH regulator is preferably at least one of citric acid, lactic acid, glutamic acid, aspartic acid, taurine, glycine, phosphoric acid, polyphosphoric acid and pyrophosphoric acid.
The propellant is preferably at least one of nitrogen, carbon dioxide, dimethyl ether, propane and isobutane.
The preparation method of the scalp hair dry cleaning powder comprises the following steps:
(1) adding a pH regulator into deionized water, and stirring until the pH regulator is completely dissolved to obtain a mixed solution 1;
(2) adding polyalcohol, a humectant and a conditioner into the mixed solution obtained in the step (1), and dispersing uniformly to obtain a mixed solution 2;
(3) adding a modified aluminum-based MOF material and an excipient into the mixed solution 2 obtained in the step (2), and dispersing until a uniform powdery product is obtained;
(4) and (3) filling the powdery product obtained in the step (3) and a propellant into an aerosol can in a packaging mode of a spray preparation to obtain the dry cleaning powder for scalp and hair containing the modified aluminum-based MOF material.
When the dry cleaning powder for scalp and hair contains the preservative, the preservative is added in the step (1).
When the dry cleaning powder for scalp and hair contains essence, the essence is added into the mixed solution obtained in the step (1) in the step (2).
The rotation speed of the dispersion in the step (3) is preferably 3000 rpm.
The application method of the dry cleaning powder for scalp and hair comprises the following steps: directly spraying the dry cleaning powder for scalp and hair on the hair, mechanically kneading until the dry cleaning powder for scalp and hair is uniformly distributed on the hair, and finally combing by a comb.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the Al-MOF material modified by the zinc compound has the advantages that the specific surface area and the pore volume are obviously improved and the adsorption performance of the material is greatly improved on the premise of not changing the crystal form of the Al-MOF material.
(2) The Al-MOF material modified by the zinc compound has greatly improved bacteriostatic ability, excellent inhibitory ability on malassezia, obvious inhibitory ability on harmful floras such as malassezia and the like, and capability of preventing the breeding of dandruff.
(3) The scalp and hair dry powder product containing the modified aluminum-based MOF material avoids the defects that starch or modified starch has poor oil adsorption capacity and is easy to remain on hair to cause hair tangling and collapse, and the experience feeling of the product is higher.
(4) The characteristics of the modified aluminum-based MOF material are not influenced by ionic characteristics, and even if the hair is not washed by water, the scalp can be dry and comfortable, the hair is not wet, static electricity is reduced, and the hair can be better combed.
(5) The scalp and hair dry powder product containing the modified aluminum-based MOF material has good stability, namely the modified aluminum-based MOF material has good compatibility with the rest components in the formula.
(6) The safety and irritation evaluation results show that the scalp and hair care dry powder product containing the modified aluminum-based MOF material has no safety risk.
(7) The modified aluminum-based MOF material can obviously improve the oil control capability of the formula in the formula.
(8) The modified aluminum-based MOF material in the formula has strong adsorption capacity on the pollution sources of the skin protection, such as heavy metal, oxidation rancidity odor of grease and the like, and reduces the deposition of the pollution sources of the skin protection on the skin protection.
Drawings
FIG. 1 is an XRD pattern of a modified aluminum-based MOF material.
FIG. 2 is a graph showing the results of treating a hair switch with the commercial dry powder product of comparative example 2.
FIG. 3 is a graph showing the results of treating hair tresses with the dry cleaning powder for scalp hair prepared according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The reagents and methods used in the examples are those commonly used in the art, unless otherwise specified, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be within the scope of the invention as claimed.
Example 1
Preparation of modified aluminum-based MOF material (also called modified Al-MOF material)
(1) Adding 133.34g (1mol) of anhydrous aluminum chloride, 166.13g (1mol) of terephthalic acid and 2000ml of N, N-dimethylformamide into an ultrasonic stirrer, wherein the ultrasonic power is 25KHz, the stirring speed is 250rpm, and stirring and ultrasonic are carried out until the mixture is uniformly mixed to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 140 ℃ at a gradient of 2 ℃/min, adding 0.27g of zinc oxide whisker (purchased from national drug group chemical reagents, Inc.), reacting at a constant temperature of 130-150 ℃ for 8h, and starting ultrasound (25KHz) every 30min during the reaction, wherein each time is 5 min; after the reaction is finished, cooling to 26 ℃, and filtering to obtain a modified Al-MOF material primary product;
(3) and (3) washing the primary modified Al-MOF material product obtained in the step (2), washing the primary modified Al-MOF material product for 3 times by using N, N-dimethylformamide, then washing the primary modified Al-MOF material product for 2 times by using acetone, and then washing the primary modified Al-MOF material product for 3 times by using deionized water. And then calcining the mixture for 5 hours in a 300 ℃ nitrogen atmosphere tube furnace for activation, and freeze-drying the mixture for 3 hours at 10Pa and-50 ℃ to obtain the modified Al-MOF material (named as modified Al-MOF material A). The modified Al-MOF material A is in the form of dry powder, has the purity of 99.2 percent and the moisture content of 0.1 percent, and is subjected to element analysis (the same below) by an EDS (energy dispersive spectroscopy) spectrometer, and the obtained element mass percentages are shown in Table 4:
TABLE 4
Figure BDA0002516454750000071
Secondly, preparing an unmodified Al-MOF material: the procedure was essentially the same as in the first part, except that no zinc oxide whiskers were added in step (2).
Third, detection
1. The modified Al-MOF material A and the unmodified Al-MOF material were measured with a specific surface area and pore structure analyzer (Micromeritics 3Fles, USA Michelle) and the specific surface areas and pore size structures obtained are shown in Table 5 below:
TABLE 5
SBET(m2/g) SInt(m2/g) VTotal(cm2/g) VMicro(cm2/g)
Unmodified Al-MOF materials 1200±100 950±15 0.5±0.12 0.4±0.08
Modified Al-MOF Material A 1350±50 980±10 0.65±0.01 0.50±0.01
It can be seen that the specific surface area and pore diameter ratio of the zinc-doped aluminum-based MOF material (modified Al-MOF material a) is increased unmodified, indicating that the adsorption performance of the modified Al-MOF material a is better.
2. And (3) stability detection:
diluting the modified Al-MOF material A into 1% (w/v) aqueous dispersion by using water, standing for 30 days at the temperature of 48 ℃, and observing XRD crystal form results at different times.
The XRD pattern of the modified Al-MOF material A which is allowed to stand for 30 days is shown in figure 1. Comparing XRD patterns of the modified Al-MOF material A which is stood for 30 days with XRD patterns of the modified Al-MOF material A which is stood for 0 day, wherein crystal forms of the modified Al-MOF material A are not different. As can be seen, the modified Al-MOF material has good water stability.
3. Bacteriostatic ability test
Escherichia coli (E.coli), staphylococcus aureus (S.aureus) and malassezia closely related to dandruff are used as test strains, the bacteriostatic ability of the modified Al-MOF material A of 1% (w/v) is inspected by a bacteriostatic circle method, the test strains are all from the innovation center of green functional daily chemical products of the Huanan collaborative innovation institute (Escherichia coli (E.coli) ATCC25922, staphylococcus aureus (S.aureus) ATCC6538 and malassezia CMCC (F) Y17), the contrast is 1% (w/v) unmodified Al-MOF material and 1% (w/v) zinc oxide whisker, and the judgment standard is as follows: the diameter of the bacteriostatic circle is more than 7mm, the bacteriostatic action is judged to be available, and the diameter is less than or equal to 7mm, the bacteriostatic action is not judged to be available.
The results are as follows:
TABLE 6
Figure BDA0002516454750000081
The bacteriostasis test result shows that the Al-MOF material modified by the zinc element has obviously improved inhibition capability on escherichia coli, staphylococcus aureus and malassezia, especially has an inhibition effect on the malassezia, and has an important significance on controlling dandruff.
Example 2 preparation of different modified Al-MOF materials
Preparation of modified Al-MOF material B
Essentially the same procedure as part of example 1, except that: the molar ratio of organic ligand (terephthalic acid) to soluble aluminium salt (anhydrous aluminium chloride) was 2: 1.
The obtained modified Al-MOF material B is in the form of dry powder, the purity is 99.2%, the moisture content is 0.1%, and the mass percentages of elements are as follows:
TABLE 7
Figure BDA0002516454750000082
The indexes of the specific surface area and the pore diameter structure of the modified Al-MOF material B are as follows:
TABLE 8
Figure BDA0002516454750000083
Preparation of modified Al-MOF material C
The procedure is essentially the same as in the first part of example 1, except that: the molar ratio of organic ligand (terephthalic acid) to soluble aluminium salt (anhydrous aluminium chloride) was 1.5: 1.
The obtained modified Al-MOF material C is in the form of dry powder, the purity is 99.2%, the moisture content is 0.1%, and the mass percentages of elements are as follows:
TABLE 9
Figure BDA0002516454750000091
Indexes of specific surface area and pore diameter structure of the modified Al-MOF material C are as follows:
watch 10
SBET(m2/g) SInt(m2/g) VTotal(cm2/g) VMicro(cm2/g)
Modified Al-MOF material C 1365±30 988±2 0.68±0.01 0.53±0.01
Preparation of modified Al-MOF material D
The procedure is essentially the same as in the first part of example 1, except that: the molar ratio of organic ligand (terephthalic acid) to soluble aluminium salt (anhydrous aluminium chloride) is 1.2:1
The obtained modified Al-MOF material D is in the form of dry powder, the purity is 99.6%, the moisture content is 0.06%, and the element mass percentages are as follows:
TABLE 11
Figure BDA0002516454750000092
Indexes of specific surface area and pore diameter structure of the modified Al-MOF material D are as follows:
TABLE 12
SBET(m2/g) SInt(m2/g) VTotal(cm2/g) VMicro(cm2/g)
Modified Al-MOF Material D 1345±15 980±10 0.64±0.01 0.52±0.01
EXAMPLE 3 preparation of Dry scalp Hair washing powder
The formula is as follows:
watch 13
Figure BDA0002516454750000093
Figure BDA0002516454750000101
The components used meet the requirements of technical specification 2015 edition of cosmetic safety.
Secondly, the preparation process is as follows:
(1) adding benzoic acid and citric acid into deionized water, and stirring until the benzoic acid and the citric acid are completely dissolved to obtain a mixed solution 1;
(2) sequentially adding propylene glycol, betaine, methoxy PEG/PPG-25/4 polydimethylsiloxane and essence into the mixed solution obtained in the step (1), and dispersing uniformly to obtain a mixed solution 2;
(3) adding the modified Al-MOF material A and silica silylate into the mixed solution 2 obtained in the step (2), and stirring and dispersing at a high speed of 3000rpm until a uniform powdery product is obtained;
(4) filling the powdery product obtained in the step (3) and nitrogen into an aerosol can in a packaging mode of a spray preparation to obtain the scalp and hair dry-cleaning powder containing the modified Al-MOF material.
The use method comprises the following steps:
when the scalp hair dry-cleaning powder is used, the aerosol spray head is directly aligned to the hair, the hair is pressed, the dry-cleaning powder in the aerosol tank is sprayed out under the action of the propellant and attached to the hair, the dry powder is uniformly distributed on the hair by mechanical rubbing, and finally the hair is combed by a comb.
EXAMPLE 4 preparation of Dry scalp Hair washing powder
The formula is as follows:
TABLE 14
Figure BDA0002516454750000102
Figure BDA0002516454750000111
The components used meet the requirements of technical specification 2015 edition of cosmetic safety.
Secondly, the preparation process is as follows:
(1) adding sodium benzoate and lactic acid into deionized water, and stirring until the sodium benzoate and the lactic acid are completely dissolved to obtain a mixed solution 1;
(2) sequentially adding 1, 3-butanediol, chitin, methoxy PEG-/PPG-7/3 aminopropyl polydimethylsiloxane and essence into the mixed solution obtained in the step (1), and dispersing uniformly to obtain a mixed solution 2;
(3) adding the modified Al-MOF material B and polydimethylsiloxane silica silylate into the mixed solution 2 obtained in the step (2), and stirring and dispersing at a high speed of 3000rpm until a uniform powdery product is obtained;
(4) filling the powdery product obtained in the step (3) and carbon dioxide into an aerosol can in a packaging mode of a spray preparation to obtain the scalp and hair dry-cleaning powder containing the modified Al-MOF material.
Third, the application method is the same as example 3.
EXAMPLE 5 preparation of Dry scalp Hair washing powder
The formula is as follows:
watch 15
Serial number Components Ratio (%)
1 Deionized water 11
2 Glycerol 8
3 Modified Al-MOF material C 8
4 Silica dimethyl silylate 8
5 Hydrolyzed chitin (molecular weight 3W daltons, degree of deacetylation 90%) 4
6 Methoxy amino terminated polydimethylsiloxane/silsesquioxane copolymers 4
7 Essence 0.08
8 Potassium sorbate 0.4
9 Glutamic acid 0.08
10 Nitrogen gas 56.44
The components used meet the requirements of technical specification 2015 edition of cosmetic safety.
Secondly, the preparation process is as follows:
(1) adding potassium sorbate and glutamic acid into deionized water, and stirring until the potassium sorbate and the glutamic acid are completely dissolved to obtain a mixed solution 1;
(2) sequentially adding glycerol, hydrolyzed chitin, methoxy amino-terminated polydimethylsiloxane/silsesquioxane copolymer and essence into the mixed solution obtained in the step (1), and dispersing uniformly to obtain a mixed solution 2;
(3) adding the modified Al-MOF material C and silica dimethyl silylate into the mixed solution 2 obtained in the step (2), and stirring and dispersing at a high speed of 3000rpm until a uniformly powdery product is obtained;
(4) and (3) filling the powdery product obtained in the step (3) and nitrogen into an aerosol can in a packaging mode of a spray preparation to obtain the scalp and hair dry powder product containing the modified Al-MOF material.
Third, the application method is the same as example 3.
EXAMPLE 6 preparation of Dry scalp Hair washing powder
The formula is as follows:
TABLE 16
Figure BDA0002516454750000121
The components used meet the requirements of technical specification 2015 edition of cosmetic safety.
Secondly, the preparation process is as follows:
the preparation method of the scalp and hair cleaning product containing the modified Al-MOF material comprises the following steps:
(1) adding potassium sorbate and lactic acid into deionized water, and stirring until the potassium sorbate and the lactic acid are completely dissolved to obtain a mixed solution 1;
(2) sequentially adding sorbitol, chitosan mono-succinamide, trimethoxysilyl polydimethylsiloxane and essence into the mixed solution obtained in the step (1), and dispersing uniformly to obtain a mixed solution 2;
(3) adding the modified Al-MOF material D and silica silylate into the mixed solution 2 obtained in the step (2), and stirring and dispersing at a high speed of 3000rpm until a uniform powdery product is obtained;
(4) filling the powdery product obtained in the step (3) and carbon dioxide into an aerosol can in a packaging mode of a spray preparation to obtain a scalp and hair dry powder product containing the modified Al-MOF material.
Third, the application method is the same as example 3.
Comparative example 1
This comparative example is essentially the same as example 3, except that no modified Al-MOF material was added.
Comparative example 2
This comparative example is essentially the same as example 4, except that no modified Al-MOF material was added.
Comparative example 3
This comparative example is essentially the same as example 5, except that no modified Al-MOF material was added.
Comparative example 4
This comparative example is essentially the same as example 6, except that no modified Al-MOF material was added.
Comparative example 5
This comparative example is essentially the same as example 3, except that an Al-MOF material which has not been modified by the zinc element (i.e., the unmodified Al-MOF material prepared in example 1) is added.
Comparative example 6
This comparative example is essentially the same as example 4, except that an Al-MOF material that is not modified by the zinc element (i.e., the unmodified Al-MOF material prepared in example 1) is added.
Evaluation of safety
The reference method comprises the following steps: chapter six toxicology test method of cosmetic safety technical Specification 2015 edition: skin irritation/Corrosion test-5.4 multiple skin irritation test procedures the dry scalp hair cleaning powder prepared in examples 3-6 of the present application was tested. The results are as follows:
TABLE 17
Sample (I) Integral mean value of skin irritation intensity Results
Dry powder prepared in example 3 0 Has no irritation
Example 4 preparation of a Dry powder 0 Has no irritation
Dry powder prepared in example 5 0 Has no irritation
Example 6 preparation of a Dry powder 0 Has no irritation
The safety evaluation result shows that the dry cleaning powder for scalp and hair containing the modified Al-MOF material has high safety and no irritation to skin.
Selection of volunteers
According to the declaration of helsinki, the volunteer's choice follows the medical and ethical standards of human testing, all of which must be voluntary by the volunteer himself and sign an informed consent prior to testing. The volunteer needs to inform the volunteer of the purpose, possible benefit, potential risks and problems of the test and the associated rights and obligations before signing an informed consent. Several volunteers selected in this study combined inclusion and exclusion criteria.
The inclusion criteria for volunteers included: the age is 18-65 years old;
exclusion criteria include that any of the following items are to be excluded: women in gestation or lactation and six months postpartum; suffering from a severe systemic disease, immunodeficiency, or autoimmune disease; the test area has been subjected to skin treatment, cosmetic or other tests that may affect the outcome; those suffering from active allergic disease; those with high constitutional sensitivity; hormone-like drugs or immunosuppressive agents have been used within a month; now or during approximately 3 months, additional tests were performed on the same site.
And (3) efficacy verification:
first, oil control efficacy
The dry scalp hair cleaning powder prepared in examples 3 to 6 and comparative examples 1 to 6 was tested by using a skin oil tester (instrument model: Sebumeter SM815) manufactured by germany couage + khazaka (ck), and the specific steps were as follows: before using the dry powder product, a skin oil tester is used for parallelly measuring the skin oil content of 2 times in a scalp measuring area, the 2 times of measuring parts are adjacent, and the average value is taken as the measured value of the area at the moment. Measuring the skin oil and fat amount of the corresponding scalp area according to the method at preset time (0.5 h, 2h and 4h after use) after using the product, taking an average value as a measured value of the area at the time point, carrying out average distribution test on 20 volunteers, and taking an average value of 2 volunteers. The results are shown below.
Table 18: scalp oil content test results (unit: mu g/cm)2)
Figure BDA0002516454750000141
Figure BDA0002516454750000151
From the scalp oil content test results, it can be seen that the scalp hair dry-cleaning powder prepared in examples 3 to 6 can significantly reduce the scalp oil content, and compared with examples 1 to 4, the oil control capability is relatively poor because no modified Al-MOF material is added. Compared with the examples 3-4, the oil control capability of the Al-MOF material which is not modified by the zinc element is weaker than that of the Al-MOF material added in the comparative examples 5-6, which is probably the result that the modified material prepared in the examples not only has excellent adsorption capability, but also has good antibacterial performance.
Second, sensory evaluation
The scalp hair dry-cleaning powders of examples 3 to 6 and comparative examples 1 to 6 were used to evaluate the odor and greasiness of hair for 0.5h, 4h and 8h, respectively, and comparative example 1 was a commercial dry powder product (starch-containing product) without any product, comparative example 2 was a commercial dry powder product, and the volunteers did not clean hair for 2 days. The number of volunteers was 24, the test was equally distributed, and a group of 2 persons was averaged.
Evaluation criteria: no off-flavor/greasy, slight off-flavor/greasy +, moderate off-flavor/greasy + +, severe off-flavor/greasy + + +; the dryness, conditioning and comfort are divided into four grades of excellent, good, medium and poor.
The detection results are as follows:
watch 19
Figure BDA0002516454750000152
Figure BDA0002516454750000161
From the results of sensory evaluation, the scalp and hair dry-cleaning powder containing the modified Al-MOF material can obviously reduce the peculiar smell and greasy feeling of the scalp and the hair, because the modified Al-MOF material adsorbed on the scalp and the hair can adsorb sebum, and the bad smell caused by the oxidative rancidity of the sebum is reduced. Compared with the commercial dry powder product, the dry powder product containing the modified Al-MOF material has obviously improved opsonization and entanglement of the hair.
The sensory evaluation result shows that the scalp and hair dry-cleaning powder containing the modified Al-MOF material has obvious drying effect and styling function, and the generated mechanism is mainly that the modified Al-MOF material adsorbed on the scalp and hair can adsorb sebum, and the bacteriostatic test shows that the scalp and hair dry-cleaning powder has good inhibition capability on malassezia and inhibits the generation of excessive sebum.
Thirdly, testing the fluffy degree of the hair after combing:
the hair tresses were treated with the commercial dry powder product of comparative example 2 and the dry powder for scalp hair obtained in example 3, respectively, and the results are shown in fig. 2 and 3. Therefore, the defects that the starch or modified starch has poor oil adsorption capacity and is easy to remain on the hair to cause hair tangling and collapse are overcome, and the experience feeling of the product is higher.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a modified aluminum-based MOF material is characterized by comprising the following steps:
(1) uniformly mixing soluble aluminum salt, organic ligand and organic solvent to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 130-150 ℃, adding a zinc compound, reacting at a constant temperature for 5-12 h, and performing ultrasonic treatment in the period; after the reaction is finished, cooling to room temperature, and filtering to obtain a modified Al-MOF material primary product;
(3) washing, activating and drying the modified Al-MOF material primary product obtained in the step (2) to obtain a modified aluminum-based MOF material;
the organic ligand in the step (1) is terephthalic acid;
the zinc compound in the step (2) is zinc oxide whisker.
2. The method according to claim 1, wherein the soluble aluminum salt in step (1) is one or both of aluminum nitrate and aluminum chloride;
the organic ligand and the soluble aluminum salt in the step (1) are mixed according to the molar ratio of (1-2): 1, calculating the mixture ratio;
the organic solvent in the step (1) is N, N-dimethylformamide;
the addition amount of the zinc compound in the step (2) is calculated according to the mass of 0.1-1.5% of the aluminum element of the zinc element;
the washing in the step (3) is sequentially washing by using N, N-dimethylformamide, acetone and deionization.
3. A modified aluminum-based MOF material prepared by the method of claim 1 or 2.
4. Use of the modified aluminum-based MOF material of claim 3 in hair products.
5. Use according to claim 4, wherein said hair products comprise dry scalp hair cleaning powders, fluffy hair powders.
6. The dry cleaning powder for the scalp and the hair is characterized by comprising the following components in percentage by mass: 5.0-10.0% of polyol, 5.0-10.0% of the modified aluminum-based MOF material of claim 3, 5.0-10.0% of an excipient, 0.5-5.0% of a humectant, 0.5-5.0% of a conditioner, 0.05-0.1% of a pH regulator and 50.0-60.0% of a propellant.
7. A scalp and hair dry-cleaning powder according to claim 6, further comprising one or both of a perfume and a preservative.
8. Dry scalp and hair cleaning powder according to claim 6, characterized in that the polyol is at least one of propylene glycol, glycerol, sorbitol, xylitol, 1, 3-butylene glycol, caprylyl glycol, hexylene glycol and pentylene glycol;
the excipient is at least one of silica silylate, silica dimethylsilylate, silica polydimethylsiloxane silylate, aluminum starch octenyl succinate, sodium starch octenyl succinate, hydrolyzed corn starch and octenyl succinate;
the humectant is at least one of betaine, chitin, hydrolyzed chitin, hydroxypropyl chitosan, hydroxyethyl chitosan, myristoyl/PCA chitosan, carboxybutyl chitosan, carboxymethyl chitosan succinamide, chitosan PCA salt, chitosan mono succinamide, chitosan glycolate and chitosan lactate;
the conditioning agent is at least one of methoxy PEG/PPG-25/4 polydimethylsiloxane, methoxy PEG-/PPG-7/3 aminopropyl polydimethylsiloxane, methoxy amino-terminated polydimethylsiloxane/silsesquioxane copolymer and trimethoxysilyl polydimethylsiloxane;
the pH regulator is at least one of citric acid, lactic acid, glutamic acid, aspartic acid, taurine, glycine, phosphoric acid, polyphosphoric acid and pyrophosphoric acid;
the propellant is at least one of nitrogen, carbon dioxide, dimethyl ether, propane and isobutane.
9. A method for preparing a dry powder for scalp hair according to any one of claims 6 to 8, comprising the steps of:
(1) adding a pH regulator into deionized water, and stirring until the pH regulator is completely dissolved to obtain a mixed solution 1;
(2) adding polyalcohol, a humectant and a conditioner into the mixed solution 1 obtained in the step (1), and dispersing uniformly to obtain a mixed solution 2;
(3) adding the modified aluminum-based MOF material of claim 3 and an excipient into the mixed solution 2 obtained in step (2), and dispersing until a uniformly powdery product is obtained;
(4) and (3) filling the powdery product obtained in the step (3) and a propellant into an aerosol can in a packaging mode of a spray preparation to obtain the dry cleaning powder for scalp and hair containing the modified aluminum-based MOF material.
10. The preparation method according to claim 9, wherein when the dry cleaning powder for scalp and hair contains preservatives, the preservatives are added in the step (1);
when the dry cleaning powder for scalp and hair contains essence, the essence is added into the mixed solution 1 obtained in the step (1) in the step (2).
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