阅读说明：本技术 一种含有铝基MOFs材料的抑菌去屑组合物及制备方法与应用 (Antibacterial and anti-dandruff composition containing aluminum-based MOFs material, and preparation method and application thereof ) 是由 何嫦娥 李清 陈英燕 于 2020-05-29 设计创作，主要内容包括：本发明公开了一种含有铝基MOFs材料的抑菌去屑组合物及制备方法与应用。该组合物由以下成分组成：铝基MOFs材料2～5份、壳多糖或其衍生物2～5份、植物低聚糖2～5份、悬浮剂0.1～1份、溶剂4～93.9份。本发明通过将前述成分混合,得到含有铝基MOFs材料的抑菌去屑组合物。该组合物稳定性好,使用简单；长期使用,不会造成头发和头皮的不良影响,无耐药性,能够平衡头皮油脂,改善头皮的健康状态。(The invention discloses a bacteriostatic and anti-dandruff composition containing an aluminum-based MOFs material, and a preparation method and application thereof. The composition consists of the following components: 2-5 parts of aluminum-based MOFs material, 2-5 parts of chitin or derivatives thereof, 2-5 parts of plant oligosaccharide, 0.1-1 part of suspending agent and 4-93.9 parts of solvent. The antibacterial and anti-dandruff composition containing the aluminum-based MOFs material is obtained by mixing the components. The composition has good stability and simple application; after long-term use, the hair conditioner does not cause adverse effects on hair and scalp, has no drug resistance, and can balance scalp grease and improve the health state of scalp.)

1. An antibacterial and anti-dandruff composition containing an aluminum-based MOFs material is characterized by comprising the following components in parts by mass:

2. bacteriostatic desquamation composition containing aluminium-based MOFs materials according to claim 1, characterized in that:

the aluminum-based MOFs material is prepared by 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.

3. Bacteriostatic desquamation composition containing aluminium-based MOFs materials according to claim 2, characterized in that:

the soluble aluminum salt in the step (1) is one or two of aluminum nitrate and aluminum chloride;

the organic ligand in the step (1) is terephthalic acid;

the organic solvent in the step (1) is N, N-dimethylformamide;

the zinc compound in the step (2) is 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.

4. Bacteriostatic desquamation composition containing aluminium-based MOFs materials according to claim 3, characterized in that:

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 addition amount of the zinc compound is calculated according to the mass of 0.1-1.5 percent of the aluminum element of the zinc element.

5. Bacteriostatic desquamation composition containing aluminium-based MOFs materials according to claim 2, characterized in that:

the mixing in the step (1) is to stir the mixture under an ultrasonic state until the mixture is uniform;

the temperature rise in the step (2) is realized by gradient temperature rise;

the ultrasonic treatment in the step (2) is carried out for 4-6 min every 30 min;

the frequency of ultrasonic treatment in the step (2) is 20-30 KHz;

the washing in the step (3) is sequentially washing by using N, N-dimethylformamide, acetone and deionized water;

the activation in the step (3) is heating activation;

the drying in the step (3) is freeze drying.

6. Bacteriostatic desquamation composition containing aluminium-based MOFs materials according to claim 5, characterized in that:

the power of the ultrasonic wave is 20-30 KHz;

the stirring speed is 200-300 rpm;

the gradient temperature rise speed is 1-3 ℃/min;

the heating and activating conditions are that the raw materials are calcined in a nitrogen atmosphere tube furnace at the temperature of 250-350 ℃ for 4-6 hours;

the freeze drying condition is drying for 2-4 h at 8-12 Pa and-40-60 ℃.

7. Bacteriostatic desquamation composition containing aluminium-based MOFs materials according to claim 1, characterized in that:

the derivative is at least one of water-soluble chitin quaternary ammonium salt and water-soluble chitin polymer;

the plant oligosaccharide is at least one of stachyose, raffinose, isomaltulose, lactulose, fructo-oligosaccharide, xylo-oligosaccharide, galacto-oligosaccharide, isomalto-oligosaccharide, gentiooligosaccharide, soybean oligosaccharide and hydrogenated starch hydrolysate;

the starch in the hydrogenated starch hydrolysate comprises potato starch, cassava starch, corn starch, wheat starch, pea starch, oat starch, kudzu starch, mung bean seed starch, red bean starch and rice starch;

the suspending agent is at least one of carbomer, xanthan gum, hydroxypropyl starch phosphate, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose;

the solvent is a mixture of water and polyhydric alcohol.

8. The preparation method of the bacteriostatic and antidandruff composition containing the aluminum-based MOFs material according to any one of claims 1 to 7, characterized by comprising the following steps: the composite material is prepared by uniformly mixing an Al-MOF material, chitin or derivatives thereof, plant oligosaccharide and a solvent.

9. The preparation method of the bacteriostatic and antidandruff composition containing the aluminum-based MOFs according to claim 8, characterized by comprising the following specific steps:

1) adding the suspending agent into a solvent, and fully and uniformly dissolving to obtain a mixture A;

2) adding chitin or its derivative into the mixture A under stirring, and stirring to dissolve uniformly to obtain mixture B;

3) adding an Al-MOF material into the mixture B in a stirring state, stirring until the mixture B is uniformly mixed, and standing for 12-36 hours at the temperature of 0-5 ℃ to obtain a mixture C;

4) and after the mixture C returns to the room temperature, adding plant oligosaccharide into the mixture C under the stirring state, and uniformly mixing to obtain the antibacterial and anti-dandruff composition containing the aluminum-based MOFs material.

10. The use of the bacteriostatic and antidandruff composition containing the aluminum-based MOFs according to any one of claims 1 to 7, wherein the bacteriostatic and antidandruff composition comprises: the bacteriostatic and anti-dandruff composition containing the aluminum-based MOFs material is directly applied to hair and scalp care; or the bacteriostatic and anti-dandruff composition containing the aluminum-based MOFs material is added into cleaning and maintenance products for use.

Technical Field

The invention belongs to the field of daily cosmetics, and particularly relates to a bacteriostatic and anti-dandruff composition containing an aluminum-based MOFs material, and a preparation method and application thereof.

Background

The surface of human scalp and the internal structure of scalp form a complete ecosystem, and the surface has secretions, dust, dirt, various bacteria and the like of sebaceous glands. The scalp is an active tissue which is constantly renewed and aged and is easy to change under the influence of the outside, the excreted secretion is accumulated on the surface of the scalp through normal metabolism, bacteria, dust mites and the like on the surface of the scalp feed on small fine crumbs and scalp metabolites falling from the skin of a human body, and the fungi take the dust mites and the human dandruff as main sources of nutrition in turn, so that a miniature ecosystem is formed on the human scalp. It is generally considered that dermatophytes symbiotic to humans, such as dermatophytes like pityriasis ovalis, enter hair follicles of hairs if their growth is unbalanced, and anaerobic metabolism thereof increases the decomposition rate of epidermal cells, thereby causing exfoliation of the epidermis to produce dandruff. The production of dandruff creates conditions for the growth and reproduction of microorganisms, and further stimulates the scalp to cause pruritus. The addition of a proper anti-dandruff agent with sterilizing and bacteriostatic abilities into shampoo is a main way for preventing and treating dandruff.

The antidandruff agents are mainly classified into the following 3 types according to different action mechanisms: keratolytic agents, cytostatic agents and antimicrobial agents.

The cuticle exfoliant removes damaged epidermal cells in the cuticle by desquamation to achieve the effect of removing dandruff, mainly comprises salicylic acid, sulfur and tar, and has the defect of strong irritation and certain damage to skin; and has limited dandruff removing effect, and long-term use can destroy the epidermal structure, disturb the balance of the epidermis, and cause skin allergy and pruritus.

Cytostatic agents, mainly inhibiting cell replication, depend on their activity in reducing the rate of replacement of the stratum corneum cells, and also on improving the normal physiological processes of keratinization and desquamation, commonly selenium sulphide, with the restoration of the length of the regeneration cycle of the cells. The dandruff remover has the defects that the clinical symptoms of dandruff cannot be well controlled, the irritation is high, coarse hair can be brought in shampoo, and the problems of alopecia, decoloration and the like can be caused if the dandruff remover is not washed thoroughly.

An antimicrobial agent which inhibits dandruff formation by inhibiting or disrupting the formation of microbial entities, the antidandruff effect of which depends on whether the number of malassezia on the scalp is reduced or controlled. With the progressive clarification of the pathogenic mechanism of malassezia, antimicrobial agents have found widespread use in anti-dandruff products. At present, Zinc Pyrithione (ZPT), pyridone ethanolamine salt (OCT), dipyrithione (BPT), hexamidine dihydroxyethyl sulfonate, climbazole, ketoconazole and the like with high use rate belong to antimicrobial preparations. However, the dandruff removing agent does not perfectly solve the problem of dandruff, for example, ZPT and OCT have the phenomenon of unstable light, and the problems of dry hair and the like can be caused after long-term use; the climbazole and ketoconazole have the problems of drug resistance and the like.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a bacteriostatic and anti-dandruff composition containing an aluminum-based MOFs material.

The invention also aims to provide a preparation method of the bacteriostatic and antidandruff composition containing the aluminum-based MOFs material.

The invention also aims to provide application of the bacteriostatic and anti-dandruff composition containing the aluminum-based MOFs material.

The purpose of the invention is realized by the following technical scheme: an antibacterial and anti-dandruff composition containing an aluminum-based MOFs material comprises the following components in parts by mass:

the aluminum-based MOFs material is a crystal material with a periodic network structure formed by self-assembling polydentate organic ligands containing oxygen or nitrogen atoms and aluminum ions, and is a hybrid coordination polymer combining the stability of inorganic matters and the multiple modifiability of organic matters; 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 units and organic ligands of terephthalic acid are bridged with each other, and a net is formed by the alternate and ordered arrangement of triangular and hexagonal pore canalsThe diameters of the channels are respectively

And

preferably prepared by 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 ℃.

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.

The derivative is preferably at least one of water-soluble chitin quaternary ammonium salt and water-soluble chitin polymer;

the water-soluble chitin quaternary ammonium salt is obtained by reacting chitin with a cationic etherifying agent; more preferably, the chitosan is prepared according to the steps in the document 'Zhang Mei Yun et al. preparation of quaternary ammonium salt chitosan and application thereof in antibacterial paper [ J ]. Chinese paper making, 2008,27(2): 14-17', wherein the ratio of the chitin to the cationic etherifying agent is 1: 3.5-4.5, and reacting for 6-8 h at 75 ℃.

The water-soluble chitin quaternary ammonium salt has a cation substitution degree of 0.45-0.65 and a viscosity-average molecular weight of (0.5-0.8) × 10⁴g/mol。

The cation etherifying agent is preferably at least one of 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride, 2, 3-epoxypropyl trimethyl ammonium chloride, 2, 3-dihydroxypropyl trimethyl ammonium chloride and 2-hydroxypropyl trimethyl ammonium chloride.

The chitin is preferably 0.8 × 10⁴～1.2×10⁴g/mol of chitin with a degree of deacetylation of at least 70%, more preferably a molecular weight of 1.0 × 10⁴g/mol, degree of deacetylation 80% chitin.

The water-soluble chitin polymer is obtained by performing free radical copolymerization reaction on chitin and monomers; more preferably prepared according to the preparation conditions of the literature 'Tang Xinghua et al, CTS-AM-DMC strong cationic natural polymeric flocculant [ J ]. Water treatment technology, 2005,31(9): 52-55'.

The viscosity-average molecular weight of the water-soluble chitin polymer is (0.8-1.2) × 10⁶g/mol。

The monomer is at least one of cationic monomer, nonionic monomer, anionic monomer and zwitterionic monomer.

The cationic monomer is preferably at least one of dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride.

The nonionic monomer is preferably at least one of acrylamide, methacrylamide, methyl acrylate and methyl methacrylate.

The anionic monomer is preferably acrylic acid.

The zwitterionic monomer is preferably 2-acrylamido-2-methylpropanesulfonic acid.

The water-soluble chitin polymer is preferably obtained by copolymerizing chitin, methacryloyloxyethyl trimethyl ammonium chloride and acrylamide; more preferably, the weight ratio of chitin to methacryloyloxyethyl trimethyl ammonium chloride to acrylamide is (1-2): (6-8): (3-6) proportioning and reacting.

The chitin has a molecular weight of 0.8 × 10⁴～1.2×10⁴g/mol, more preferably 1.0 × 10⁴g/mol。

The plant oligosaccharide is preferably at least one of stachyose, raffinose, isomaltulose, lactulose, fructo-oligosaccharide, xylo-oligosaccharide, galacto-oligosaccharide, isomalto-oligosaccharide, gentiooligosaccharide, soybean oligosaccharide and hydrogenated starch hydrolysate;

the starch in the hydrogenated starch hydrolysate comprises potato starch, cassava starch, corn starch, wheat starch, pea starch, oat starch, kudzu starch, mung bean seed starch, red bean starch and rice starch; preferably corn starch.

The suspending agent is preferably at least one of carbomer, xanthan gum, hydroxypropyl starch phosphate, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.

The suspending agent is prepared from commercially available cosmetic grade raw materials and meets the requirements of technical specification 2015 edition of cosmetic safety.

The solvent is preferably a mixture of water and polyhydric alcohol; more preferably a solvent obtained by mixing water and a polyhydric alcohol in a volume ratio of 1: 1.

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 preparation method of the bacteriostatic and anti-dandruff composition containing the aluminum-based MOFs material comprises the following steps: uniformly mixing an Al-MOF material, chitin or derivatives thereof, plant oligosaccharide and a solvent to obtain the chitosan-metal organic framework; preferably comprises the following specific steps:

1) adding the suspending agent into a solvent, and fully and uniformly dissolving to obtain a mixture A;

2) adding chitin or its derivative into the mixture A under stirring, and stirring to dissolve uniformly to obtain mixture B;

3) adding an Al-MOF material into the mixture B in a stirring state, stirring until the mixture B is uniformly mixed, and standing for 12-36 hours at the temperature of 0-5 ℃ to obtain a mixture C;

4) and after the mixture C returns to the room temperature, adding plant oligosaccharide into the mixture C under the stirring state, and uniformly mixing to obtain the antibacterial and anti-dandruff composition containing the aluminum-based MOFs material.

The rotation speed of the mixing in the step 1) is preferably 800-1200 rpm.

The rotating speed of stirring in the step 2) is preferably 400-800 rpm.

The rotating speed of stirring in the step 3) is preferably 200-400 rpm.

The time for standing in step 3) is preferably 24 hours.

The rotating speed of the stirring in the step 4) is preferably 100-200 rpm.

The room temperature is 0-40 ℃; preferably 20-30 ℃; more preferably 24 to 28 DEG C

The bacteriostatic and anti-dandruff composition containing the aluminum-based MOFs material can be directly applied to hair and scalp care, and when the bacteriostatic and anti-dandruff composition containing the aluminum-based MOFs material is used, the bacteriostatic and anti-dandruff composition containing the aluminum-based MOFs material is directly and uniformly applied to the hair and scalp; can also be added into cleaning and maintaining products.

The invention has the following beneficial effects:

(1) the antibacterial and anti-dandruff composition provided by the invention is simple in preparation process and has good antibacterial and anti-dandruff effects.

(2) The composition provided by the invention has good stability and is simple to use; after long-term use, the hair conditioner does not cause adverse effects on hair and scalp, has no drug resistance, and can balance scalp grease and improve the health state of scalp.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.