CN108192154A - A kind of external preparation for skin hydrogel material - Google Patents

A kind of external preparation for skin hydrogel material Download PDF

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Publication number
CN108192154A
CN108192154A CN201810116653.4A CN201810116653A CN108192154A CN 108192154 A CN108192154 A CN 108192154A CN 201810116653 A CN201810116653 A CN 201810116653A CN 108192154 A CN108192154 A CN 108192154A
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fruit
glue
glossy privet
shell
skin
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王子昂
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212Face masks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/042Gels
    • 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
    • A61K8/73Polysaccharides
    • 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
    • A61K8/73Polysaccharides
    • A61K8/733Alginic acid; Salts 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/736Chitin; Chitosan; Derivatives 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0023Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • A61L26/0066Medicaments; Biocides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • A61L26/008Hydrogels or hydrocolloids
    • 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
    • A61Q17/005Antimicrobial preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04Alginic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

Azure ocean is not only richly stored with resource, also huge economic benefit is hidden, the polymerizate of the raw materials such as chitin and acrylic acid that the seed glue and ocean shrimp, crab that the present invention is extracted using alginate, the vegetable seeds of marine algae extraction extract, add in compounding antiseptic, natural environmental-protective has been made in processing, the external preparation for skin hydrogel with good moisturizing, antibiotic effect.The hydrogel material of the present invention is by weight percentage, comprising sodium alginate 0.5 5%, fruit of glossy privet glue 0.5 8%, modified acrylic polymer 0.5 5%, aqueous solution of propylene glycol 75.5 99.5%, compounding antiseptic 0.01 2%, the wherein volume fraction of aqueous solution of propylene glycol is 2 15%.The present invention has studied the humectant properties of sodium alginate, fruit of glossy privet glue, modified acrylic polymer, and compared with sodium alginate, fruit of glossy privet glue, modified acrylic polymer is used alone, gel combination of the invention has increasing significantly in terms of moistening effect;With compounding antiseptic instead of traditional anti-corrosive antibacterial component, for the anti-corrosion of gel, the safe and efficient antibacterial of hydrogel material is realized.

Description

A kind of external preparation for skin hydrogel material
Technical field
The invention belongs to biomedicine fields, particularly belong to a kind of external preparation for skin hydrogel material.
Background technology
Azure ocean is not only richly stored with resource, also hides huge economic benefit, how to make full use of sea The foreign diversified biomaterial of development of resources, there is important researching value.
Biological medicine is one of industry of state key development, and biomaterial is green, environmental-friendly, resource-effective due to it The features such as, just gradually becoming the leading industry for leading another of contemporary world scientific and technical innovation and economic development new.Preparation has The biomaterial of multi-efficiency, and it is the hot spot studied instantly to use it for pharmaceutical sanitary field.Utilize biology base high water solubility Hydrogel prepared by molecule is carried in biomedicine field, such as tissue bulking material, cartilage material, drug coating and drug Body etc. is widely applied, and has the advantages such as good biologically inert and biocompatibility.
However, current hydrogel material still has, raw material scope of selecting material is limited, and the application field of gel rubber material is single, Underuse marine resources;Replenishing water and preserving moisture effect is general, lacks specific skin moisture-keeping performance study;Anti-corrosive antibacterial component list One, the technical problems such as effect unobvious.Develop biological source more effect hydrogel materials and expand its application field have it is important Meaning.
Invention content
The present invention is carried using the alginate of marine algae extraction, the seed glue of vegetable seeds extraction and ocean shrimp, crab The polymerizate of the raw materials such as the chitin and acrylic acid that take, adds in compounding antiseptic, and natural environmental-protective has been made, and has in processing Good moisturizing, the external preparation for skin hydrogel of antibiotic effect.The materials and application domain of gel rubber material have been expanded, have taken full advantage of ocean Resource has pushed ocean fine chemistry industry industrial expansion.
The hydrogel of the present invention includes sodium alginate, fruit of glossy privet glue, modified acrylic polymer, aqueous solution of propylene glycol, sea Mosanom is prepared using limnetic dry kelp by alkaline extraction, and fruit of glossy privet glue is prepared using Fruits of Ligustrum Lucidum Ait by water extraction, and modified third The raw materials such as the chitin that olefin(e) acid polymer is extracted by acrylic acid with ocean shrimp, crab are prepared by polymerisation, hydrogel tool There are good gel-forming property and moistening effect, have the function of to improve skin moisture content.With sodium alginate, glossy privet is used alone Sub- glue, modified acrylic polymer are compared using traditional gel combination, and gel combination of the invention is in moistening effect Aspect tool increases significantly.
Due in the hydrogel raw material of the present invention rich in microorganism growth needed for nutrient, microorganism in environment once into Enter, i.e., can breed rapidly, destroy the organoleptic quality of product, damage the health of user, therefore inhibit the numerous of microorganism in gel It is vital to grow.Inhibit the continuous understanding of microbial mechanism with the necessity to antibacterial and to antiseptic, it is traditional Antiseptic, preservative are faced with various queries and challenge, and main negative effect is that irritation is slightly larger, to the sensitization rate of skin It is high.The present invention is with compounding antiseptic instead of traditional anti-corrosive antibacterial component such as parabens, isothiazolinone, non-stimulated nothing It is skin allergy, safe and efficient antibacterial.
The present invention provides a kind of external preparation for skin hydrogel materials, by weight percentage, include sodium alginate 0.5- 5%th, fruit of glossy privet glue 0.5-8%, modified acrylic polymer 0.5-5%, aqueous solution of propylene glycol 75.5-99.5%, compounding antibacterial The volume fraction of agent 0.01-2%, wherein aqueous solution of propylene glycol are 2-15%, and the water is deionized water, and the sodium alginate takes From marine algae, fruit of glossy privet glue is derived from Fruits of Ligustrum Lucidum Ait, the chitin and third that modified acrylic polymer is ocean shrimp, crab is extracted The polymerizate of olefin(e) acid.
Relative to conventional hydrogels material, hydrogel material of the invention has the following effects that:
1st, materials Yu Haiyang, base material abundance realize efficiently using for marine resources, have pushed the hair of ocean fine chemistry industry Exhibition.
2nd, the humectant properties of sodium alginate, fruit of glossy privet glue, modified acrylic polymer are had studied, be used alone sodium alginate, Fruit of glossy privet glue, modified acrylic polymer are compared using traditional gel combination, and gel combination of the invention is in moisturizing Tool increases significantly in terms of effect.
3rd, with compounding antiseptic, for the anti-corrosion of gel, hydrogel material is realized instead of traditional anti-corrosive antibacterial component It is safe and efficient antibacterial.
The preparation method of external preparation for skin hydrogel of the present invention is as follows:
1st, the preparation of sodium alginate
A kind of method of the sodium alginate extraction from limnetic dry kelp, step are as follows:
Rounding strain limnetic dry kelp, deionized water wash away surface silt, natural airing, chopping.The above-mentioned kelps of 60g are taken, are placed in 1L In 0.lmol/L dilute hydrochloric acid, soak at room temperature 10h.Deionized water washes away surface extract, appropriate 3%Na2CO3Solution impregnates 3min, Kelp epidermis is removed, deionized water, which is cleaned, to be placed in 2L flasks.Add in 420mL 2%Na2CO3Solution continues in 40 DEG C of water-baths 2h, mixing speed 400rpm/min are stirred, extracting solution in the pasty state, adds in 180mL deionized waters dilution extracting solution, continues to stir 1h successively with 200,300 mesh sock filtrations, takes filtrate to add in 1mol/L HC1 solution and neutralizes excessive lye under agitation To pH=7, extracting solution A is obtained.It is in acidity to continue to instill 1mol/L HC1 into A to adjust solution, seaweed acid gel is precipitated, with 200 Mesh sock filtration, deionized water washing is multiple, washes away hydrochloric acid accompanying by seaweed acid gel.Appropriate 10%NaOH solution is added dropwise not Disconnected stirring, making alginic acid, all dissolving is converted into sodium alginate.
2nd, the preparation of fruit of glossy privet glue
A kind of preparation method of fruit of glossy privet glue, step are as follows:
According to the weight ratio fruit of glossy privet:Water is 1:10-1:30 ratio after the fruit of glossy privet is uniformly mixed with deionized water, controls water Ranging from 75-95 DEG C extraction 15-60min of bath temperature, after filtering, supernatant is the extraction of fruit of glossy privet glue to the leaching liquor of gained Liquid.
3rd, the preparation of modified acrylic polymer
A kind of modified acrylic polymer preparation method, step are as follows:
(1) chitosan that molecular weight is 100kDa, deacetylation is 90% is dissolved in the acetic acid that percentage by volume is 1% In aqueous solution, itaconic acid aqueous solution is added dropwise, chitosan initial concentration is 20mg/mL, and the initial concentration of itaconic acid is 0.1mol/L, The molar ratio of itaconic acid and amino in chitosan molecule is 1.2:18h is stirred to react at 1,70 DEG C, is made after reaction With excessive NaHCO3The pH to 8 of reaction solution is adjusted, is then precipitated using ethyl alcohol, solid component is collected by filtration, through dry To substance I
(2) in terms of mass fraction, I 3 parts of substance, 5 parts of ethyl methacrylate, 12 parts of acrylic acid are weighed, 1 part of acrylamide is thick Plain 1 part of phenol, 1.5 parts of trimethylolpropane are uniformly mixed and prepare monomer mixture;
(3) take the monomer mixture of 10 weight % that seed pre-emulsion is prepared with 1.5 parts of lauryl sodium sulfate emulsifications;
(4) in terms of mass fraction, 2 parts of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 25 parts of deionized waters are added in into reaction kettle In, it opens stirring and increases the temperature of reaction system, 0.03 part of ammonium persulfate is added in after temperature reaches 80 DEG C, stablizes 15min Afterwards, seed pre-emulsion was dripped in 30 minutes, stablizes 30min, residual monomer mixture and 0.15 part of ammonium persulfate is molten Liquid drips off in 4h, is warming up to 85 DEG C of reaction 2h, is cooled to 35 DEG C, is neutralized with ammonia spirit, cooling discharge after heat preservation 30 minutes Obtain modified acrylic polymer;In the step (4), by weight percentage, a concentration of the 2.0% of ammonium persulfate solution;Institute State a concentration of the 7.0% of ammonia spirit.
4th, the preparation of antiseptic is compounded
A kind of preparation method for compounding antimicrobial composition, step are as follows:
II 1%-50% of substance, benzoaric acid 1%-50%, 2 phenylethyl alcohol 10%-50% are weighed by weight percentage, Compounding antimicrobial composition is obtained, the structure of wherein substance II is as follows:
5th, the preparation of external preparation for skin hydrogel
(1) propylene glycol, deionized water are measured respectively, are configured to the aqueous solution of propylene glycol of 2-15% volume fractions;
(2) by weight percentage, compounding antiseptic 0.01-2% is taken, adds in appropriate above-mentioned aqueous solution of propylene glycol, 70-90 DEG C of water It is heated in bath, compounding antiseptic is made all to dissolve, take out cooling;
(3) by weight percentage, sodium alginate 0.5-5%, fruit of glossy privet glue 0.5-8%, modified acroleic acid polymerization are weighed respectively Object 0.5-5% adds in the aqueous solution of propylene glycol of step (1), stirring and dissolving;
(4) solution of step (2) and (3) is uniformly mixed, adds the aqueous solution of propylene glycol of step (1) to 100%, stirring is equal It is even, 4h is placed to get to external preparation for skin hydrogel.
The fruit of glossy privet has the function of nourishing liver and kidney, improving eyesight black hair.Be mainly used for dizziness and tinnitus, soreness and weakness of waist and knees, poliosis, Mesh is secretly unknown etc..Modern pharmacological research also found that it has the function of reducing blood lipid, hypoglycemic.It there is no at present about fruit of glossy privet glue Research report, the present invention are extracted fruit of glossy privet glue, and characterize its main chemical compositions, realize deeply grinding for Chinese medicine for the first time Hair.
In one embodiment, the present invention is extracted fruit of glossy privet glue and its main component is characterized, and another The performance of keeping humidity of fruit of glossy privet glue is tested in a embodiment, realizes the multi-efficiency exploitation of Chinese medicine.
In one embodiment, the present invention has studied the skin moisture-keeping performance of hydrogel, tests fruit of glossy privet glue, sea respectively The performance of keeping humidity of the skin of the external preparation for skin hydrogel of mosanom, modified acrylic polymer and the present invention, research find this The plastic component of invention is respectively provided with preferable moistening effect, moisture of skin can be effectively prevent to scatter and disappear, while a variety of plastic components Compounding can play synergistic effect so that moisture-keeping efficacy is strengthened.
With age or climate change, the cuticula of skin will seem dry, dark and gloomy due to water shortage, be periodically flesh Skin supplement large quantity of moisture and adequate nutrition substance, can make skin restore elasticity and gloss, so as to reach beauty and anti-aging Effect.The facial mask of currently used unwoven fabric type is that the base materials such as non-woven fabrics, fabric, paper are immersed in facial mask liquid mostly, It is directly used after taking-up, this facial mask is since moisture evaporation is fast, and nutriment can not fully be combined with skin, in use Nutrient solution is easily dripped from base material, cause waste with it is inconvenient for use.
In one embodiment, the present invention provides a kind of moisturizing gel masks for including above-mentioned hydrogel.In the present invention Hydrogel in add in grease, surfactant, the components such as preservative, a kind of moisturizing gel mask is made.The present invention provides A kind of moisturizing gel mask, by weight percentage, composition are as follows:Sodium alginate 0.1-3%, fruit of glossy privet glue 0.5-2.5%, change Property acrylate copolymer 0.5-4%, propylene glycol 2-8%, compounding antiseptic 0.1-0.5%, sunflower seed oil 0.1-0.5%, ovum Phosphatidase 0 .1-1.0%, cysteine 0.5%, panthenol 1.0-2.0%, deionized water surplus.
The hydrogel moisture saver mask can be that skin supplements large quantity of moisture, and good biocompatibility is non-stimulated to skin, and viscosity is moderate.
A kind of moisturizing gel mask, preparation method are as follows:
(1) grease, lecithin, propylene glycol are dissolved in a small amount of water for use;
(2) it is sodium alginate, fruit of glossy privet glue, modified acrylic polymer is soluble in water, add in compounding antiseptic, cysteine, Panthenol stirs evenly;
(3) oil-soluble component with water-soluble components is uniformly mixed, obtains gel mask, be sealed.
Water soluble polymer is widely applied for hydrogel prepared by raw material in biomedicine field, hydrogel Dressing is due to good water penetration, oxygen permeability, absorbing wound exudate without adhesion, helping to reach wound healing Purpose, be widely used in clinic.However, existing aerogel dressing lacks the moisturizing ingredient of definite functions, water holding capacity Antibacterials that are limited, also can not used locally in hydrogel increase the danger of wound infection, also increase frequently The workload of dressing.
In one embodiment, the present invention provides a kind of wound dressings for including above-mentioned gel rubber material.By sodium alginate, Fruit of glossy privet glue and modified acrylic polymer add in compounding antiseptic by cross-linking radiation, obtain biocompatibility it is good, can be with Absorb a large amount of moisture, can effective over the surface of a wound, maintain wound surface enclosed humidity wound dressing, with anti-inflammatory it is antibacterial, The effect of wound healing, by zoopery demonstrate hydrogel material it is definite the effect of.
In one embodiment, the present invention provides a kind of gel wound dressings, and by weight percentage, composition is such as Under:Sodium alginate 1.0-4.0%, fruit of glossy privet glue 1.0-3.0%, modified acrylic polymer 0.5-4.0%, propylene glycol 5- 10%th, compounding antiseptic 0.1-1%, polyethylene glycol 0.1-8%, deionized water surplus.
The preparation method of the gel wound dressing is as follows:
(1) fruit of glossy privet glue is dissolved in distilled water, solution A is made;
(2) modified acrylic polymer is dissolved in distilled water, solution B is made;
(3) merge solution A and solution B, be uniformly mixed, add in sodium alginate, polyethylene glycol, propylene glycol and hydrogel solution is made;
(4) after hydrogel solution is stored at room temperature, flow regime is heated to, the aquagel membrane that thickness is 1-5mm is made, cycle is cold Freeze-thaw melts processing 2-4 times;At room temperature60C ° of gamma-radiation or the crosslinking of high-power electron beam x ray irradiation x, dosage 60-110kGy/h;
(5) the aquagel membrane natural draft drying of cross-linking radiation, room temperature in vacuo is dry or is freeze-dried, and the degree of dehydration is 30- 100%, the aquagel membrane radiosterilization of dehydration, the partially dried hydrogel of disinfection is aseptically immersed in the antibacterial containing compounding In the distilled water of agent, swelling behavior takes out up to after balancing, and seals, 0 DEG C of Cord blood.After comparing predose, outside hydrogel See darker, in interconnected cellular hole, between 50-500 μ ms, TG temperature has significantly to be carried hole diameter It is high.
The water soluble polymer of synthesis such as polyethylene glycol has the advantages of deriving from a wealth of sources, cheap.Water-soluble height Molecule such as seed glue, chitin, chitosan etc. have unique biocompatibility and bioactivity, can be as aerogel dressing Active ingredient.When radiation method prepares medical hydrogel dressings, added in water-soluble polymer solution a certain proportion of natural poly- Object is closed, the biocompatibility of hydrogel can be improved;Meanwhile natural polymer degrade under actinism after can be filled in it is solidifying In glue network gap, play the role of improving gel strength.The addition of moisturizer propylene glycol can be very good to improve medical water-setting The flexibility and water-retaining property of glue dressing.The addition compounding antiseptic in medical hydrogel dressings, can have aerogel dressing and control Treatment acts on.Content of dispersion in hydrogel can be very big, and after the drug consumption of gel surface, the drug inside gel can be by moving It moves and diffusion is constantly supplemented, realize the sustained release of drug, alleviate the burden of the frequent dressing of medical staff, also reduce Because dressing leads to the danger of wound bacterium infection not in time.
Hydrogel needs to ensure normal solvent content, to realize its excellent moisturizing, antibacterial action, to need sealed storage, Usual hydrogel material is individually hermetically sealed, be easy to cause the waste of packaging material.And gel rubber material has certain viscosity, makes When being applied with common coating device, gel easily condenses in the outflow of applicator head opening obstruction gel when reusing, and In the case that coating device installs cap body additional to completely cut off air reserve, gel and the cap body of applicator head opening remaining are in direct contact appearance It easily bonds, opens cap body difficult.
Based on conventionally-coated device when using this gel the existing above problem, the present invention also provides one kind comprising this The scalable applying device of the external preparation for skin hydrogel is invented, which specially coats inventive gel product, can Effectively overcome hydrogel material storage and inconvenient problem with use.
Applying device is by applying device shell 1, scalable coating part 2, bottle 3, spring 4,5 groups of sliding shoe in the application Divide into, described device shell 1 for small diameter cylinders shell and shell cylind er with large diameter, two sections of different cylindrical shells of diameter are connected to one Rise, small diameter cylinders shell both sides are respectively opened there are one bar-shaped trough 6, and small diameter cylinders shell opener end is equipped with external screw thread, can with equipped with interior The cap body cooperation of screw thread seals opening, and small diameter cylinders shell is more than internal wall thickness close to openend position wall thickness, so as to small straight Boss is formed with inside diameter cylindrical shell, shell cylind er with large diameter openend is equipped with internal thread;The scalable coating part 2 is divided for thin-walled Section and heavy wall section, thin segment is the cylindrical shell that V-type is processed into one section of open end section, and heavy wall section internal diameter is identical with thin segment, Wall thickness is more than the wall thickness of thin segment, so that 2 middle part of scalable coating part is formed with boss, rear wall section is each close to boss position both sides Bayonet 8 there are one opening;The sliding shoe 5 is made of latch post and arc panel, latch post may pass through the bar-shaped trough 6 be inserted into it is described In bayonet 8, so as to which arc panel be made to be fitted in the small diameter cylinders shell outside wall surface of coating head shell 1, along the small of applying device shell 1 When diameter cylindrical shell outside wall surface slides arc panel, latch post can be driven to be slided in bar-shaped trough 6, so as to drive scalable coating part 2 in 1 internal slide of applying device shell to stretch out or retract;The spring 4 is arranged on 1 internal boss face of coating head shell and can Between flexible 2 exterior boss face of coating piece, when sliding sliding shoe 5 makes the scalable coating part 2 be in stretching state, spring 4 is pressed Contracting, unclamps sliding shoe 5, and scalable coating piece 2 is retracted under the effect of 4 elastic force of spring;3 end of bottle is equipped with and applying device The shell cylind er with large diameter internal thread of shell 1 matches the external screw thread of sum, and bottle 3 is internally provided with inwardly protruded annular convex platform, to limit The motion range that scalable coating part 2 bounces back is made, bottle 3 is used to be loaded with the hydrogel 9 for applying application.
In use, the dynamic sliding shoe 5 of set stretches out scalable coating part 2, liquid is flow to through scalable 2 inner passage of coating part The V-shaped shape in section is processed into openend, the openend of scalable coating part 2, and tip portion facilitates the coating of liquid, coating After the completion, sliding shoe 5 is unclamped, scalable coating part 2 is retracted under the effect of 4 elastic force of spring, and coating liquid is remained at and can be stretched In the inner passage of contracting coating part 2, will not overflow will not pollute applying device shell 1, easy to use.Scalable applying device Use, stabilize the water content of hydrogel material so that external preparation for skin hydrogel has more stable skin moisturization, It is easy to be cohesive to solve the problems, such as that gel is in direct contact with cap body, simultaneous retractable head can repeatedly use, and save packaging Material.
Applying device of the present invention is also applicable to the easily cohesive gel-like or viscous liquid class being sealed The preservation and use of product.
Description of the drawings
The fractionation part structure diagram of the scalable coating head of Fig. 1 the application;
Sectional view when the scalable coating head of Fig. 2 the application is in contraction state;
Sectional view when the scalable coating head of Fig. 3 the application is in stretching state;
In figure:1- coating head shells, the scalable coating pieces of 2-, 3- bottles, 4- springs, 5- sliding shoes, 6- bar-shaped troughs, 7- are convex Platform, 8- bayonets, 9- hydrogels, 10- cap bodies.
Specific embodiment
The present invention provides a kind of external preparation for skin hydrogel biological material, and those skilled in the art can use for reference present disclosure, It is suitably modified technological parameter.In particular, it should be pointed out that all similar substitutions and modifications are for a person skilled in the art It will be apparent that they are considered as being included in the present invention.The method of the present invention and application are carried out by preferred embodiment Description, related personnel can significantly not depart from the content of present invention, methods herein and application changed in spirit and scope It is dynamic or suitably change with combining, to realize and using the technology of the present invention.
Reagent that the present invention uses, material are ordinary commercial products without specified otherwise.
The chemical composition analysis of embodiment one, fruit of glossy privet glue
The fruit of glossy privet has the function of nourishing liver and kidney, improving eyesight black hair.Be mainly used for dizziness and tinnitus, soreness and weakness of waist and knees, poliosis, Mesh is secretly unknown etc..Modern medicine study thinks that the fruit of glossy privet can inhibit treatment of the helicobacter pylori for stomach trouble, also have Inhibit the effect of purine abnormal metabolism, for the treatment of gout and hyperuricemia.Modern pharmacological research also found that it has drop Blood fat, hypoglycemic effect.It there is no the report about fruit of glossy privet glue at present.The present invention is extracted fruit of glossy privet glue, and characterize for the first time Its main chemical compositions.
Fruit of glossy privet glue preparation method is as follows:According to the weight ratio fruit of glossy privet:Water is 1:20 ratio, by the fruit of glossy privet and deionization Water is uniformly after mixing, and ranging from 85 DEG C extraction 30min of control bath temperature, after filtering, supernatant is the leaching liquor of gained Fruit of glossy privet glue extracting solution.
Fruit of glossy privet glue is mainly made of polysaccharide and protein, also containing ingredients such as a small amount of amino acid, monosaccharide.Its key component is more Sugar, protein characterization are as follows:
1st, the measure of moisture:Hypobaric drying method (GB5009.3-85)
2nd, the measure of content of ashes:Calcination method (GB5009.4-85)
3rd, the measure of protein content:
(1) total protein content:Lowry methods
(2) binding protein content:
0.5 weight % fruit of glossy privet sol solutions are prepared, 15% solution of trichloroacetic acid is added in, is added dropwise to Ph4.5, albumen while stirring Matter is precipitated completely, is centrifuged off precipitating, and supernatant measures protein to water dialysis 48h, freeze-drying with Lowry methods Content.
(3) Free protein content:
Floating preteins=total protein content-binding protein content
4th, the measure of total starches content:
Gravimetric method:Fruit of glossy privet glue 1.000g accurately is weighed, is dissolved in 200mL water.It is added in the fruit of glossy privet sol solution being completely dissolved Absolute ethyl alcohol to final concentration of alcohol is 70 weight %, is precipitated, in triplicate, then under conditions of 0.1MPa, 60 DEG C Dry 1h, then drying to constant weight at 105 DEG C, cooling is weighed, and calculates the content of total starches in sample.
5th, analysis result:
Fruit of glossy privet glue main component such as table 1
1 fruit of glossy privet glue main component of table
It can be seen that the main component of fruit of glossy privet glue is polysaccharide, there is certain moisturizing moisturizing, also contain on a small quantity Protein is capable of providing additional skin effect.
The preparation of embodiment two, external preparation for skin hydrogel
A kind of external preparation for skin hydrogel and preparation method thereof.
1st, the preparation of sodium alginate
A kind of method of the sodium alginate extraction from limnetic dry kelp, step are as follows:
Rounding strain limnetic dry kelp, deionized water wash away surface silt, natural airing, chopping.The above-mentioned kelps of 60g are taken, are placed in In 1L 0.lmol/L dilute hydrochloric acid, soak at room temperature 10h.Deionized water washes away surface extract, appropriate 3%Na2CO3Solution impregnates 3min removes kelp epidermis, and deionized water, which is cleaned, to be placed in 2L flasks.Add in 420mL 2%Na2CO3Solution, 40 DEG C of water-baths In persistently stir 2h, mixing speed 400rpm/min, extracting solution in the pasty state, adds in 180mL deionized waters dilution extracting solution, continues 1h is stirred, successively with 200,300 mesh sock filtrations, filtrate addition 1mol/L HC1 solution is taken to neutralize under agitation excessive Lye obtains extracting solution A to pH=7.It is in acidity to continue to instill 1mol/L HCl into A to adjust solution, and seaweed acid gel is precipitated, uses 200 mesh sock filtrations, deionized water washing is multiple, washes away hydrochloric acid accompanying by seaweed acid gel.Appropriate 10%NaOH solution is added dropwise And be stirred continuously, making alginic acid, all dissolving is converted into sodium alginate.
2nd, the preparation of fruit of glossy privet glue
A kind of preparation method of fruit of glossy privet glue, step are as follows:
According to the weight ratio fruit of glossy privet:Water is 1:20 ratio after the fruit of glossy privet is uniformly mixed with deionized water, controls water-bath Temperature range is 85 DEG C of extraction 30min, and after filtering, supernatant is fruit of glossy privet glue extracting solution to the leaching liquor of gained.
3rd, the preparation of modified acrylic polymer
A kind of modified acrylic polymer preparation method, step are as follows:
(1) chitosan that molecular weight is 100kDa, deacetylation is 90% is dissolved in the acetic acid that percentage by volume is 1% Rear that itaconic acid aqueous solution is added dropwise in aqueous solution, chitosan initial concentration is 20mg/mL, and the initial concentration of itaconic acid is 0.1mol/ The molar ratio of L, itaconic acid and amino in chitosan molecule is 1.2:18h is stirred to react at 1,70 DEG C, after reaction Use excessive NaHCO3The pH to 8 of reaction solution is adjusted, is then precipitated using ethyl alcohol, solid component is collected by filtration, through drying Obtain substance I;
(2) in terms of mass fraction, I 3 parts of substance, 5 parts of ethyl methacrylate, 12 parts of acrylic acid are weighed, 1 part of acrylamide is thick Plain 1 part of phenol, 1.5 parts of trimethylolpropane are uniformly mixed and prepare monomer mixture;
(3) take the monomer mixture of 10 weight % that seed pre-emulsion is prepared with 1.5 parts of lauryl sodium sulfate emulsifications;
(4) in terms of mass fraction, 2 parts of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 25 parts of deionized waters are added in into reaction kettle In, it opens stirring and increases the temperature of reaction system, 0.03 part of ammonium persulfate is added in after temperature reaches 80 DEG C, stablizes 15min Afterwards, seed pre-emulsion is dripped in 30min, stablizes 30min, by residual monomer mixture and 0.15 part of ammonium persulfate solution It was dripped off in 4 hours, is warming up to 85 DEG C of reaction 2h, is cooled to 35 DEG C, is neutralized with 0.8 part of ammonia spirit, cooled down after keeping the temperature 30min Discharge to obtain polyacrylate;In the step (4), a concentration of 2.0 weight % of ammonium persulfate solution;The ammonia spirit it is dense It spends for 7.0 weight %.
4th, the preparation of antiseptic is compounded
A kind of preparation method for compounding antimicrobial composition, step are as follows:
II 25 weight % of substance, 25 weight % of benzoaric acid, 50 weight % of 2 phenylethyl alcohol are weighed in proportion, and compounding is made Antiseptic.
5th, the preparation of external preparation for skin hydrogel
A kind of preparation method of external preparation for skin hydrogel, step are as follows:
(1) propylene glycol, deionized water are measured respectively, are configured to the aqueous solution of propylene glycol of 5% volume fraction;
(2) by weight percentage, compounding antiseptic 0.1% is taken, appropriate above-mentioned aqueous solution of propylene glycol is added in, adds in 80 DEG C of water-baths Heat makes compounding antiseptic all dissolve, and takes out cooling;
(3) by weight percentage, sodium alginate 2%, fruit of glossy privet glue 2%, modified acrylic polymer 2% are weighed respectively, are added Enter the aqueous solution of propylene glycol of step (1), stirring and dissolving;
(4) solution of step (2) and (3) is uniformly mixed, adds the aqueous solution of propylene glycol of step (1) to 100%, stirring is equal It is even, 4h is placed to get to external preparation for skin hydrogel.
The skin moisturization test of embodiment three, external preparation for skin hydrogel material
1st, raw material is tested:
(1) embodiment and comparative example prescription is as follows:
Embodiment 3-A, the hydrogel by weight percentage, include sodium alginate 2%, fruit of glossy privet glue 2%, modified acroleic acid The aqueous solution of propylene glycol surplus of polymer 2%, 5%.
Embodiment 3-B, the hydrogel by weight percentage, include sodium alginate 5%, fruit of glossy privet glue 0.5%, modified propylene The aqueous solution of propylene glycol surplus of acid polymer 0.5%, 2%.
Embodiment 3-C, the hydrogel by weight percentage, comprising sodium alginate 2%, include fruit of glossy privet glue 1%, modified third The aqueous solution of propylene glycol surplus of olefin(e) acid polymer 4%, 8%.
Comparative example 3-a, the hydrogel by weight percentage, include the aqueous solution of propylene glycol surplus of sodium alginate 6%, 5%.
Comparative example 3-b, the hydrogel by weight percentage, include the aqueous solution of propylene glycol surplus of fruit of glossy privet glue 6%, 5%.
Comparative example 3-c, the hydrogel by weight percentage, include the propylene glycol water of modified acrylic polymer 6%, 5% Solution water surplus.
Comparative example 3-d, the hydrogel by weight percentage, comprising sodium alginate 3%, fruit of glossy privet glue 3%, 5% the third two Alcohol solution surplus.
Comparative example 3-e, the hydrogel by weight percentage, comprising sodium alginate 3%, modified acrylic polymer 3%, 5% aqueous solution of propylene glycol surplus.
Comparative example 3-f, the hydrogel by weight percentage, comprising fruit of glossy privet glue 3%, modified acrylic polymer 3%, 5% aqueous solution of propylene glycol surplus.
Comparative example 3-g, the hydrogel by weight percentage, include sodium alginate 2%, fruit of glossy privet glue 2%, modified acroleic acid Polymer 2%, water surplus.
(2) preparation method of external preparation for skin hydrogel material:
According to preparation method disclosed in embodiment two, the external preparation for skin hydrogel material of embodiment and comparative example is prepared.
2nd, the skin moisture-keeping performance test of external preparation for skin hydrogel material:
(1) test equipment:German CK companies Multi-functional skin tester, model C UTOMETER DUAL MPA 580, the present invention Select skin moisture content test probe.
(2) test philosophy:Using the moisture of capacitance method test human body keratoderma, its principle is based on water and other The difference in dielectric constant of substance is notable, and according to moisture content of skin difference, the capacitance for measuring skin is different, and observed parameter can generation Table skin moisture value.
(3) test environment conditions:Test environment temperature is 22 ± 1 DEG C, and humidity is 50 ± 5%, and carries out Real-time and Dynamic Detection;
Volunteer requires:Effective volunteer at least 30 people, the age is between 16-65 Sui;Forearm test zone capacitance method skin water Divide the basic value for measuring meaning between 15-100;Without serious systemic disease, no immune deficiency or autoimmune disease person;Nothing Activity anaphylactic disease person;Previously to skin-care cosmetics without severe allergy history person;Amcinonide is not used in nearly one month Object and immunosuppressor person:To participate in other clinical test persons;Use according to regulations test medicine and all information;Own before test Volunteer should fill in informed consent form.
(4) prepare before test:Any product (cosmetics or topical drug) cannot be used within 2-3 days before recipient site.Before experiment, by Examination person needs to agree to survey in cleaning both hands forearm, with dry face tissue wiped clean.It surveys and does in subject's both hands forearm after cleaning Good measured zone label.At least 30min that sits quietly in room should be being complied with standard before official testing, it is impossible to be drunk water, forearm exposure is in Test mode is placed, and keeps loosening.
(5) testing procedure:3 × 3cm of label on the inside of left and right arm in experiment2Test area, same arm can mark multiple areas Domain, it is interregional every 1cm.Test product and blank control are randomly dispersed in left and right arm.Use capacitance method skin analyzer Carry out the measurement of tested region and control zone.Each region is according to parallel determination 15 times.First measure the blank of each test zone Paper, then by 2.0 ± 0.1mg samples/cm2Dosage, experiment is spread evenly across in trial zone using latex finger cot.It surveys respectively Amount 10,20,40,60,120min, the moisture content of skin in tested region and blank control region, the test of same volunteer by Same survey crew completes.
(6) data processing:Design decibel empirically measures the MMV values of each period.
Calculation formula is:W%=(W1-W0)/W0 × 100%
Note:W%=skin moisture contents increased percentage (MMV)
W0=skins use moisture before sample
W1=skins use moisture after sample
(7) test result such as table 2
The MMV values of 2 each period of table
By experiment it is found that the present invention sodium alginate, fruit of glossy privet glue and modified acrylic polymer be respectively provided with it is certain Moisturizing effect has preferable the effect of increasing skin moisture content.External preparation for skin hydrogel material provided by the invention, by seaweed Sour sodium, fruit of glossy privet glue and modified acrylic polymer, aqueous solution of propylene glycol compounding, by synergistic effect, produce better guarantor Wet effect has excellent moisture-keeping function, can significantly improve skin moisture content.
Example IV, the evaluation and test of the characteristic of moisturizing gel mask
1st, the preparation of sample gel mask:
(1) the raw material composition of gel mask:
Embodiment 4-A:Sodium alginate 2%, fruit of glossy privet glue 2%, modified acrylic polymer 2%, propylene glycol 3%, compounding Antiseptic 0.5%, sunflower seed oil 0.5%, lecithin 0.5%, cysteine 0.1%, panthenol 2.0%, deionized water surplus.
Embodiment 4-B:Sodium alginate 1.5%, modified acrylic polymer 3%, propylene glycol 5%, is answered at fruit of glossy privet glue 2% With antiseptic 0.2%, sunflower seed oil 0.2%, lecithin 0.6%, cysteine 0.5%, panthenol 1.0%, para hydroxybenzene first Acetoacetic ester 0.1%, deionized water surplus.
Comparative example:4-a:Carboxymethyl cellulose 2%, fruit of glossy privet glue 2%, modified acrylic polymer 2%, propylene glycol 3%, compounding Antiseptic 0.5%, sunflower seed oil 0.5%, lecithin 0.5%, cysteine 0.1%, panthenol 2.0%, deionized water surplus.
Comparative example:4-b:Sodium alginate 2%, xanthans 2%, modified acrylic polymer 2%, propylene glycol 3%, compounding antiseptic 0.5%th, sunflower seed oil 0.5%, lecithin 0.5%, cysteine 0.1%, panthenol 2.0%, deionized water surplus.
Comparative example:4-c:Sodium alginate 6%, propylene glycol 3%, compounding antiseptic 0.5%, sunflower seed oil 0.5%, lecithin 0.5%th, cysteine 0.1%, panthenol 2.0%, deionized water surplus.
Comparative example:4-d:Fruit of glossy privet glue 6%, propylene glycol 3%, compounding antiseptic 0.5%, sunflower seed oil 0.5%, lecithin 0.5%th, cysteine 0.1%, panthenol 2.0%, deionized water surplus.
Comparative example:4-e:Sodium alginate 2%, fruit of glossy privet glue 2%, modified acrylic polymer 2%, propylene glycol 3%, compounding antibacterial Agent 0.5%, caprylic/capric triglyceride 0.5%, lecithin 0.5%, cysteine 0.1%, panthenol 2.0%, more than deionized water Amount.
Comparative example:4-f:Sodium alginate 2%, fruit of glossy privet glue 2%, modified acrylic polymer 2%, ethyl alcohol 3%, compounding antiseptic 0.5%th, sunflower seed oil 0.5%, lecithin 0.5%, cysteine 0.1%, panthenol 2.0%, deionized water surplus.
(2) preparation method of moisturizing gel mask:
1. grease, lecithin, propylene glycol are dissolved in a small amount of water for use;
2. sodium alginate, fruit of glossy privet glue, modified acrylic polymer is soluble in water, add in compounding antiseptic, cysteine, general Alcohol stirs evenly;
3. oil-soluble component is uniformly mixed with water-soluble components, gel mask is obtained, is sealed in applying device.
(3) application method of gel mask:Moisturizing gel mask is spread on into skin nursing position after face cleaning, during use It can gently massage and nurse position, after 15-20min, gel mask is significantly thinning, and nutrition and moisture are transferred to skin, are removed, punching Wash clean.
2nd, the measurement result of sample gel mask physical and chemical index:
(1) viscosity:It is measured with NDJ-1 viscosimeters.The viscosity of facial mask is 10650mPas, under this viscosity, facial mask viscosity It is moderate, it is fine and smooth smooth, it is easy to spread floating out, film is uniform, tends to smear out.
(2)pH:According to GB/T 13531.1-2008, the pH of facial mask is measured.The pH at normal temperatures of facial mask be 7.02, meet cream/ The regulation of emulsus facial mask relevant criterion.
(3) drying time:0.2g film samples are weighed, uniformly spreads out on clean glass slide (25.4mm × 76.2mm), makes Film sample is uniform on glass slide, thickness is consistent;Then be placed at room temperature, treat it is tack-free until, record the dry time.Face The drying time of film is 1148 ± 30s.Too short when facial mask drying time, the effect that skin absorbs active ingredient is bad, and can be right Skin generates stronger pulling force, and skin is made to feel tight discomfort;And drying time is long, skin pore opening time is long, meeting Make skin dehydration excessive, and then influence the absorption of active ingredient.The facial mask drying time that this experiment is produced is convenient.
(4) stability:
1. heat resistance:By moisturizing gel mask after 40 DEG C are stored 30 days, visual observations find itself and the character and face before experiment Color does not generate notable difference, and no layering, oil slick phenomenon show that mask product heat resistance is preferable.
2. cold resistance:By moisturizing gel mask after 0 DEG C is stored 30 days, visual observations find itself and the character and color before experiment Notable difference is not generated, and no layering, oil slick phenomenon show that mask product heat resistance is preferable.
3. cold cycling:For moisturizing gel mask after cold cycling alternating test, visual observations find that it is apparent with nothing before experiment Difference, layering, oil slick and permeability phenomenon do not occur, and color and luster also without significant change, shows that mask product is cold-resistant hot preferable.
3rd, the measure of moisturizing gel mask performance of keeping humidity:
Skin moisture content test test has carried out the moisturizing antibacterial facial mask of the present invention using the test method of embodiment 1-3, The moisture content of skin in measurement 10,20,30,40,50,60,120min respectively, tested region and blank control region, test result Such as table 3.
Table 3:The MMV values of moisturizing gel mask each period
By experiment it is found that the moisturizing gel mask of the present invention, there is preferable the effect of increasing skin moisture content.It will be extra large Mosanom, fruit of glossy privet glue and modified acrylic polymer, aqueous solution of propylene glycol compounding, by synergistic effect, produce preferably Moistening effect;The addition of sunflower seed oil, lecithin, cysteine, panthenol improves the moisturizing effect of hydrogel so that this The moisturizing gel mask of invention has excellent moisture-keeping efficacy, can significantly improve skin moisture content.
Embodiment five, the fungistatic effect evaluation method and result for compounding antiseptic
Due to the nutrient needed for being grown in the hydrogel raw material of the present invention rich in microorganism, the microorganism in environment once enters, It can breed rapidly, destroy the organoleptic quality of product, damage the health of user, therefore the breeding of microorganism is in inhibition gel It is vital.For the present invention with compounding antiseptic instead of traditional anti-corrosive antibacterial component, non-stimulated no skin allergy, safety are high It imitates antibacterial.
1st, the preparation of sample solution:
(1) the raw material composition of sample antiseptic:
Embodiment 5-A:Substance II 25%, benzoaric acid 25%, 2 phenylethyl alcohol 50%
Embodiment 5-B:The external preparation for skin hydrogel material of 0.1g/mL 5-A, 0.1g/mL embodiments 3-A.
Comparative example 5-a:Substance II
Comparative example 5-b:Benzoaric acid
Comparative example 5-c:2 phenylethyl alcohol
Wherein, substance II is made by oneself for laboratory:
Substance II:(S)-5-phenylfuran-2(5H)-one
Yield:31.4mg (98%) .Yellow oil, 90%ee.The ee of the product was determined by HPLC.[Daicel CHIRALPAK OJ-H(0.46cm×25cm);Hexane/2-propanol=90/10;flow Rate=1.0mL/min;Detection wavelength=214nm;tR=32.724 (major), 34.253 (minor) min].[α]20 D=-1.35 (c 0.43, CHCl3), 90%ee.IR (film, cm-1):1792,1757,1495,1453,1298, 1265,1159,1088,1033,895,850,815,765,697,612.1H NMR(400MHz,CDCl3) δ 7.54 (dd, J= 5.6,1.6Hz, 1H), 7.43-7.38 (m, 1H), 7.41-7.38 (m, 2H), 7.30-7.27 (m, 1H), 6.23 (dd, J=5.6, 2.1Hz,1H),6.03-6.01(m,1H).13C NMR(101MHz,CDCl3)δ173.06,155.81,134.17,129.29, 129.00,126.45,120.90,84.34.MS(ESI+)m/z(M+Na).HRMS calcd.for(C12H12O2Na+): 183.0417,found183.0425.
(2) preparation method of sample antiseptic:
Above-mentioned raw materials are weighed by mass fraction, after being dissolved with DMSO solvents, are made into the solution for standby that mass concentration is 0.1g/mL.
2nd, actication of culture:
It takes culture dish several, pours into the culture medium tablet after 20mL sterilizings, it aseptically will be big for examination strain with scribing line Enterobacteria, staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans and aspergillus niger are accessed on corresponding plating medium, are put into In incubator, bacterium is cultivated for 24 hours at 37 DEG C, and mould cultivates 48-72h at 28 DEG C;
3rd, the preparation of strains tested suspension:
It is inoculated into respective liquid culture medium from picking single bacterium colony on the tablet after each activation, microbionation is in nutrient broth, ferment Female bacterium and mould are inoculated in potato fluid nutrient medium, respectively at cultivated in 37 DEG C, 28 DEG C of constant-temperature shaking incubators for 24 hours, 48- As original bacteria liquid after 72h, it is 10 that each original bacteria liquid, which is made containing bacterium number, with sterile saline respectively6The bacteria suspension of CFU/mL.Institute The nutrient broth stated, by every liter of calculating, raw material composition and content are as follows:Peptone 10.0g, beef extract powder 3.0g, chlorine Change sodium 5.0g, surplus is water;The potato fluid nutrient medium, by every liter of calculating, raw material composition and content are as follows: It is water that potato, which leaches powder 6.0g, glucose 20.0g, chloramphenicol 0.1g, surplus,.
4th, the measure of fungistatic effect:
On superclean bench, the solid medium after 20mL is sterilized pours into sterile petri dish tablet, after cooling in injection 100 μ L of bacteria suspension are stated, media surface is expanded to sterile spreading rod smearing, then puts sterile Oxford surface is equidistant Cup, the concentration obtained by the step of 200 μ L are injected separately into cup (1) are the solution of the embodiment and comparative example of 0.1g/mL, are done Synchronous bacteriostatic experiment carries out blank control, is put into incubator, bacterium is cultivated for 24 hours at 37 DEG C, and mould cultivates 48- at 28 DEG C 72h takes out on time, measures antibacterial circle diameter, is averaged.
5th, test result
Table 4:The fungistatic effect of Compositional type antiseptic
As can be seen from the above table, substance II, benzoaric acid, 2 phenylethyl alcohol are respectively provided with certain antibacterial work(under same concentrations Effect, the bacteriostasis of Compositional type natural antibacterial agent composition significantly better than single-activity substance, particularly its to Escherichia coli and Staphylococcus aureus has obvious inhibiting effect.The addition of hydrogel material of the present invention, there is antibacterial effect Certain castering action, it is seen that acted synergistically between hydrogel material and antiseptic of the invention, antibacterial is contributed to imitate Fruit preferably plays.
6th, anti-corrosion effect of the compounding antiseptic in gel mask
(1) a kind of gel mask of such as embodiment 4-A, is calculated, raw material composition and content are as follows by mass percentage:Sea Mosanom 2%, fruit of glossy privet glue 2%, modified acrylic polymer 2%, propylene glycol 5%, compounding antiseptic 0.5%, sunflower seed Oil 0.5%, lecithin 0.5%, cysteine 0.1%, panthenol 2.0%, deionized water surplus.
(2) test method
Using preservation challenge method of testing, tested with reference to United States Pharmacopeia (USP) method.
1st group:Not adding preservative agent
2nd group:0.5% compounding antiseptic
3rd group:0.5% methyl hydroxybenzoate
Experimental result is shown in Table 5:
Table 5:Preservative efficacy testing result
"+" indicates bacterium colony appearance in table, and "-" represents that no bacterium colony occurs.
As shown in Table 5, do not add compounding antiseptic for the 1st group, without fungistatic effect.2nd group adds 0.5% compounding antibacterial Agent, can be by equal concentration 10 in 7 days5-106The microorganism of CFU/g all inhibits, and its fungistatic effect is better than traditional anti-corrosion Antiseptic.It follows that the compounding antiseptic of the present invention has good antibacterial effect, making for traditional preservatives can be replaced With improving the safety of product.
Embodiment six, hydrogel wound dressing
The present invention is prepared for a kind of hydrogel wound dressing, investigates its skin irritation and to the new zealand rabbit Superficial bums surface of a wound Healing.The result shows that the aerogel dressing clear of preparation, viscosity is suitable, and no skin irritation simultaneously can significantly promote Into the healing of the new zealand rabbit Superficial bums surface of a wound.
1st, the preparation of hydrogel wound dressing:
By weight percentage, following substances are weighed:
Embodiment 6-A:Sodium alginate 3%, fruit of glossy privet glue 3%, modified acrylic polymer 3%, propylene glycol 8%, compounding antibacterial Agent 1%, polyethylene glycol 4%, deionized water surplus.
Comparative example 6-a:Sodium alginate 9%, propylene glycol 8%, compounding antiseptic 1%, polyethylene glycol 4%, deionized water surplus.
Comparative example 6-b:Fruit of glossy privet glue 9%, propylene glycol 8%, compounding antiseptic 1%, polyethylene glycol 4%, deionized water surplus.
Comparative example 6-c:Modified acrylic polymer 9%, propylene glycol 8%, compounding antiseptic 1%, polyethylene glycol 4%, deionization Water surplus.
Comparative example 6-d:Fruit of glossy privet glue 4.5%, propylene glycol 8%, compounding antiseptic 1%, gathers modified acrylic polymer 4.5% Ethylene glycol 4%, deionized water surplus.
Comparative example 6-e:Sodium alginate 3%, fruit of glossy privet glue 3%, modified acrylic polymer 3%, compounding antiseptic 1%, poly- second Glycol 4%, deionized water surplus.
The preparation method of the hydrogel wound dressing is as follows:
(1) fruit of glossy privet glue is dissolved in distilled water, solution A is made;
(2) modified acrylic polymer is dissolved in distilled water, solution B is made;
(3) merge solution A and solution B, be uniformly mixed, add in sodium alginate, polyethylene glycol, propylene glycol and hydrogel solution is made;
(4) after hydrogel solution is stored at room temperature, be heated to flow regime, be made thickness be 3mm aquagel membrane, circulating frozen- Melt process 3 times;At room temperature60C ° of gamma-radiation or the crosslinking of high-power electron beam x ray irradiation x, dosage 100kGy/h;
(5) the aquagel membrane natural draft drying of cross-linking radiation, room temperature in vacuo is dry or freeze-drying, the degree of dehydration are 80%, the aquagel membrane radiosterilization of dehydration, the partially dried hydrogel of disinfection is aseptically immersed in the antibacterial containing compounding In the distilled water of agent, swelling behavior takes out up to after balancing, and seals, 0 DEG C of Cord blood
2nd, the performance test of aerogel dressing:
(1) gel fraction:After hydrogel freeze-drying, using redistilled water as solvent, Soxhlet extractor extracting 30h;Gel point Gel dry weight × 100% before number=(gel dry weight after gel dry weight-extracting before extracting)/extracting.
(2) mechanical property:It is measured by 1121 tensilons of instron, tensile speed 10mm/min, batten long 20.0mm is wide 4.0mm;
(3) equilibrium water absorption:After hydrogel freeze-drying second distillation outlet capacity is absorbed at 20 DEG C;Equilibrium water absorption %=(inhales Gel dry weight before gel weight-water suction after water balance)/water suction before gel dry weight × 100%;
Table 6:The performance of aerogel dressing
3rd, skin irritation test:
New zealand rabbit 5, every 2.0-2.5kg, back shaving, the ranging from each 5 × 10cm in backbone both sides for 24 hours before experiment, inspection For skin without being damaged, skin of back is divided into 3 regions.It takes clear that good, each 1g of aerogel dressing 6-A are applied to 3cm × 3cm nonwovens On cloth, non-woven fabrics is pasted on to 1,2 areas at new zealand rabbit back respectively, applies powder contact skin, the 3rd area is blank control, is used Glassine paper covers non-woven fabrics, then is fixed with nonirritant adhesive plaster and bandage.Non-woven fabrics is removed after 6h, and administration is cleaned with warm water Position.Respectively at for 24 hours, 48h and 72h observation skin, erythema and oedema situation are recorded.
Table 7:Rabbit skin irritant experiment result
Result of the test shows that wound dressing of the invention is safe to use, no allergy and skin irritation.
4th, the Cure Study On of burn wound
Male New Zealand rabbits 80, every 2.0-2.5kg are taken, are randomly divided into 8 groups, every group 10.Each rabbit is dynamic according to clinic Object experimental burning master pattern preparation method causes 30%TBSA Superficial bums.New zealand rabbit is anaesthetized, back cleaning and sterilizing Afterwards, according to grouping situation administration, administration thickness is 3-5mm, and the surface of a wound fixed wrapping after being covered with sterile gauze prevents drug from taking off It falls, every other day dressing, until crust is completely fallen off, the surface of a wound has epithelium covering.Wherein A groups rabbit does not use any dressing, B group rabbits Application positive control gel sample (brightness Co., Ltd of Xerox of Qing get Jia Britain, lot number 123422), the C group application embodiment of the present invention The wound dressing of 6-A, the hydrogel of D, E, F, G, H application comparative example 6-a, 6-b, 6-c, 6-d, 6-e.
Zoopery the results are shown in Table 8:
Table:8:Rabbit burns rear wound healing result
From the result of zoopery, after the dressing of the hydrogel wound of the application present invention, the surface of a wound without infection phenomenons, Occur without redness.The wound dressing of the present invention is more created with obvious effects better than positive controls, can be used as general wound dressing. The healing time of the D-H group rabbit surface of a wound is significantly greater than C groups, and time difference has significant difference, the gel dressing phase with control group Than, C groups dressing because of the gel combination containing the present invention, under the conditions of existing for compounding antiseptic, more can effective nuring wound, Wound healing simultaneously shortens healing time, and dressing prepared by the present invention can play the role of acceleration to the healing of the surface of a wound.
The hydrogel wound dressing of the present invention has the gel-type vehicle and complex antimicrobials of good humectant properties, has actively Antibacterial ability, while have water content height, good water-retaining property, biological safety height, convenient drug administration, clear be easy to observation wound The characteristics of face, can meet the requirement of the various wounds of Soaking therapy, can not only be used for mild skin wound or chronic skin disease forever Long property dressing, it can also be used to the treatment of serious skin tissue injury or wound of burning.
Embodiment seven, a kind of applying device for external preparation for skin hydrogel material
Hydrogel needs to ensure normal solvent content, to realize its excellent moisturizing, antibacterial action, to need sealed storage, Usual hydrogel material is individually hermetically sealed, be easy to cause the waste of packaging material.And gel rubber material has certain viscosity, makes When being applied with common applying device, gel easily condenses in the outflow of applicator head opening obstruction gel when reusing, and In the case that applying device installs cap body additional to completely cut off air reserve, gel and the cap body of applicator head opening remaining are in direct contact appearance It easily bonds, opens cap body difficult.
Based on conventionally-coated device when using this gel the existing above problem, the present invention also provides one kind comprising this The scalable applying device of the external preparation for skin hydrogel is invented, which specially coats inventive gel product, can Effectively overcome hydrogel material storage and inconvenient problem with use.The applicator head of the present invention can be recycled for multiple times, energy saving Environmental protection.
In the application scalable applying device device by coating unit shell 1, scalable coating part 2, bottle 3, spring 4, Sliding shoe 5 forms, and described device crust of the device 1 divides for small diameter cylinders shell and shell cylind er with large diameter, the different circle of two sections of diameters Column shell links together, and small diameter cylinders shell both sides are respectively opened there are one bar-shaped trough 6, and small diameter cylinders shell opener end is equipped with outer spiral shell Line can seal opening with setting female cap body cooperation, and small diameter cylinders shell is more than interior wall close to openend position wall thickness Thickness, so as to be formed with boss inside small diameter cylinders shell, shell cylind er with large diameter openend is equipped with internal thread;The scalable painting It applies part 2 to divide for thin segment and heavy wall section, thin segment is the cylindrical shell that V-type is processed into one section of open end section, heavy wall section internal diameter Identical with thin segment, wall thickness is more than the wall thickness of thin segment, so that 2 middle part of scalable coating part is formed with boss, rear wall section is close It respectively opens there are one bayonet 8 boss position both sides;The sliding shoe 5 is made of latch post and arc panel, and latch post may pass through described Bar-shaped trough 6 is inserted into the bayonet 8, so as to which arc panel be made to be fitted in the small diameter cylinders shell outside wall surface of coating head shell 1, along painting When the small diameter cylinders shell outside wall surface of coating apparatus shell 1 slides arc panel, latch post can be driven to be slided in bar-shaped trough 6, so as to Scalable coating part 2 is driven in 1 internal slide of applying device shell to stretch out or retract;The spring 4 is arranged on outside coating head Between 2 exterior boss face of 1 internal boss face of shell and scalable coating piece, sliding sliding shoe 5 makes scalable coating part 2 be in stretching During state, spring 4 is compressed, and unclamps sliding shoe 5, and scalable coating piece 2 is retracted under the effect of 4 elastic force of spring;3 end of bottle Portion be equipped with match with the shell cylind er with large diameter internal thread of applying device shell 1 and external screw thread, bottle 3 is internally provided with inwardly protruded Annular convex platform, to limit the motion range that scalable coating part 2 bounces back, bottle 3 is used to be loaded with the hydrogel 9 for applying application.
In use, the dynamic sliding shoe 5 of set stretches out scalable coating part 2, liquid is flow to through scalable 2 inner passage of coating part The V-shaped shape in section is processed into openend, the openend of scalable coating part 2, and tip portion facilitates the coating of liquid, coating After the completion, sliding shoe 5 is unclamped, scalable coating part 2 is retracted under the effect of 4 elastic force of spring, and coating liquid is remained at and can be stretched In the inner passage of contracting coating part 2, will not overflow will not pollute applying device shell 1, easy to use.
The use of scalable applying device stabilizes the water content of hydrogel material so that external preparation for skin hydrogel has More stable skin moisturization, it is easy to be cohesive to solve the problems, such as that gel is in direct contact with cap body, simultaneous retractable head can It repeatedly uses, has saved packaging material.
Applying device of the present invention is also applicable to the easily cohesive gel-like or viscous liquid class being sealed The preservation and use of product.
It the above is only the preferred embodiment of the present invention, it is noted that those skilled in the art are come It says, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as Protection scope of the present invention.

Claims (9)

1. a kind of external preparation for skin hydrogel material by weight percentage, includes sodium alginate 0.5-5%, fruit of glossy privet glue 0.5- 8%th, modified acrylic polymer 0.5-5%, aqueous solution of propylene glycol 75.5-99.5%, compounding antiseptic 0.01-2%, wherein third The volume fraction of two alcohol solutions is 2-15%, and the water is deionized water, and the sodium alginate is derived from marine algae, the fruit of glossy privet Glue is derived from Fruits of Ligustrum Lucidum Ait, and the raw materials such as the chitin that modified acrylic polymer is ocean shrimp, crab is extracted and acrylic acid polymerize Product.
2. external preparation for skin hydrogel material as described in claim 1, which is characterized in that the preparation method of the fruit of glossy privet glue is such as Under:According to the weight ratio fruit of glossy privet:Water is 1:10-1:30 ratio after the fruit of glossy privet is uniformly mixed with deionized water, controls water-bath Temperature range is 75-95 DEG C of extraction 15-60min, and after filtering, supernatant is fruit of glossy privet glue extracting solution to the leaching liquor of gained.
3. external preparation for skin hydrogel material as described in claim 1, which is characterized in that the modified acrylic polymer Preparation method is as follows:
(1) chitosan that molecular weight is 100kDa, deacetylation is 90% is dissolved in the acetic acid that percentage by volume is 1% In aqueous solution, itaconic acid aqueous solution is added dropwise, chitosan initial concentration is 20mg/mL, and the initial concentration of itaconic acid is 0.1mol/L, The molar ratio of itaconic acid and amino in chitosan molecule is 1.2:18h is stirred to react at 1,70 DEG C, is made after reaction With excessive NaHCO3The pH to 8 of reaction solution is adjusted, is then precipitated using ethyl alcohol, solid component is collected by filtration, through dry To substance I
(2) in terms of mass fraction, I 3 parts of substance, 5 parts of ethyl methacrylate, 12 parts of acrylic acid are weighed, 1 part of acrylamide is thick Plain 1 part of phenol, 1.5 parts of trimethylolpropane are uniformly mixed and prepare monomer mixture;
(3) take the monomer mixture of 10 weight % that seed pre-emulsion is prepared with 1.5 parts of lauryl sodium sulfate emulsifications;
(4) in terms of mass fraction, 2 parts of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 25 parts of deionized waters are added in into reaction kettle In, it opens stirring and increases the temperature of reaction system, 0.03 part of ammonium persulfate is added in after temperature reaches 80 DEG C, stablizes 15min Afterwards, seed pre-emulsion was dripped in 30 minutes, stablizes 30min, residual monomer mixture and 0.15 part of ammonium persulfate is molten Liquid drips off in 4h, is warming up to 85 DEG C of reaction 2h, is cooled to 35 DEG C, is neutralized with ammonia spirit, cooling discharge after heat preservation 30 minutes Obtain modified acrylic polymer;In the step (4), by weight percentage, a concentration of the 2.0% of ammonium persulfate solution;Institute State a concentration of the 7.0% of ammonia spirit.
4. external preparation for skin hydrogel material as described in claim 1, wherein compounding antiseptic is, by weight percentage, object II 1%-50% of matter, benzoaric acid 1%-50%, 2 phenylethyl alcohol 10%-50%, the structure of wherein substance II are as follows:
5. a kind of moisturizing gel mask, which is characterized in that include the external preparation for skin water-setting as described in any one of claim 1-4 Glue material.
6. a kind of moisturizing gel mask as claimed in claim 5, which is characterized in that by weight percentage, composition is as follows:Sea Mosanom 0.1-3.0%, fruit of glossy privet glue 0.5-2.5%, modified acrylic polymer 0.5-4.0%, propylene glycol 2-8%, compounding Antiseptic 0.1-0.5%, sunflower seed oil 0.1-0.5%, lecithin 0.1-1.0%, cysteine 0.5%, panthenol 1.0- 2.0%th, deionized water surplus.
7. a kind of hydrogel wound dressing, which is characterized in that include the external preparation for skin as described in seeking any one of 1-4 such as claim Hydrogel material.
8. hydrogel wound dressing as claimed in claim 7, which is characterized in that by weight percentage, composition is as follows:Seaweed Sour sodium 1.0-4.0%, fruit of glossy privet glue 1.0-3.0%, modified acrylic polymer 0.5-4.0%, propylene glycol 5-10%, compounding are anti- Microbial inoculum 0.1-1%, polyethylene glycol 0.1-8%, deionized water surplus.
A kind of 9. applying device for coating such as claim 1-8 any one of them hydrogels, which is characterized in that the painting Coating apparatus is made of applying device shell (1), scalable coating part (2), bottle (3), spring (4), sliding shoe (5), the painting Coating apparatus shell (1) is divided into small diameter cylinders shell and shell cylind er with large diameter, and two sections of different cylindrical shells of diameter link together, small Diameter cylindrical shell both sides are respectively opened there are one bar-shaped trough (6), and small diameter cylinders shell opener end is equipped with external screw thread, can with equipped with internal thread Cap body (10) cooperation seal opening, small diameter cylinders shell is more than internal wall thickness close to openend position wall thickness, so as to it is small directly Boss is formed with inside diameter cylindrical shell, shell cylind er with large diameter openend is equipped with internal thread;The scalable coating part (2) is divided into thin Wall section and heavy wall section, thin segment are the cylindrical shell that V-type is processed into one section of open end section, heavy wall section internal diameter and thin segment phase Together, wall thickness is more than the wall thickness of thin segment, so as to be formed with boss in the middle part of scalable coating part (2), rear wall section is close to boss position It respectively opens there are one bayonet (8) both sides;The sliding shoe (5) is made of latch post and arc panel, and latch post may pass through the bar shaped Slot (6) is inserted into the bayonet (8), so as to which arc panel be made to be fitted in the small diameter cylinders shell outside wall surface of coating head shell (1), edge When the small diameter cylinders shell outside wall surface of applying device shell (1) slides arc panel, latch post can be driven sliding in bar-shaped trough (6) It is dynamic;The spring (4) is arranged between coating head shell (1) internal boss face and scalable coating piece (2) exterior boss face;Institute State bottle (3) end be equipped with match with the shell cylind er with large diameter internal thread of applying device shell (1) and external screw thread, in bottle (3) Portion is equipped with inwardly protruded annular convex platform, and to limit the motion range of scalable coating part (2) retraction, bottle (3) is for containing Equipped with the hydrogel (9) for applying application.
CN201810116653.4A 2018-02-08 2018-02-08 A kind of external preparation for skin hydrogel material Pending CN108192154A (en)

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