CN103110535B - Sunscreening granule with TiO2-HA core-shell structure as well as preparation method and application thereof - Google Patents

Sunscreening granule with TiO2-HA core-shell structure as well as preparation method and application thereof Download PDF

Info

Publication number
CN103110535B
CN103110535B CN201310046158.8A CN201310046158A CN103110535B CN 103110535 B CN103110535 B CN 103110535B CN 201310046158 A CN201310046158 A CN 201310046158A CN 103110535 B CN103110535 B CN 103110535B
Authority
CN
China
Prior art keywords
granule
core
tio
shell structure
tio2
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201310046158.8A
Other languages
Chinese (zh)
Other versions
CN103110535A (en
Inventor
徐首红
李相晔
刘欢
李成亮
刘洪来
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Laibo Bio-chemical Co Ltd
East China University of Science and Technology
Original Assignee
Shanghai Laibo Bio-chemical Co Ltd
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Laibo Bio-chemical Co Ltd, East China University of Science and Technology filed Critical Shanghai Laibo Bio-chemical Co Ltd
Priority to CN201310046158.8A priority Critical patent/CN103110535B/en
Publication of CN103110535A publication Critical patent/CN103110535A/en
Application granted granted Critical
Publication of CN103110535B publication Critical patent/CN103110535B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention provides a core-shell structure granule with sunscreening and moisturizing effects. The granule is composed of an inner core inorganic TiO2 granule and a transparent hyaluronic acid (HA) polymer gel outer layer. Nano TiO2 is an important inorganic ultraviolet screening agent, has the functions of reflecting and scattering ultraviolet rays and can achieve the physical sunscreening effect; however, nano TiO2 can easily enter pores owning to too small grain size and is harmful to a human body, and the problems of dry skin and damage to skin are caused, so that wide application of the nano TiO2 in the field of cosmetics is prevented. According to the sunscreening granule, core-shell structure granular assembly design is carried out on the TiO2 and biological polymer gel, transparent hyaluronic acid gel is modified on the surface of the inorganic TiO2 granule, skin moisturizing effect and affinity function of the granule are enhanced, and dual effect of sunscreening and beautifying are achieved; besides, after HA gel is coated, visible light transmittance of solution also can be increased, grain size of the granule is increased, and dispersion stability of the granule is improved, so that aggregation is avoided. The granule of the core-shell structure can be applied to high-end cosmetics such as sunscreen cream and sunscreen emulsion.

Description

TiO 2the sun-proof granule of-HA nucleocapsid structure, its preparation method and application
Technical field
The invention belongs to cosmetic field, be specifically related to inorganic-organic core-shell structure microgranule, more specifically relate to the TiO as sun-prevention component 2-HA core-shell structure particles.
Background technology
TiO 2be a kind of quasiconductor, its energy gap (Eg) is 3.0eV, and the ultraviolet radiation that is less than 400nm when wavelength is at TiO 2when upper, the electronics in valence band can absorb ultraviolet and be excited on conduction band, produces electron-hole pair, therefore TiO simultaneously 2there is the ultraviolet function of absorption.The nano-TiO using at cosmetic field 2crystal formation is generally rutile-type, is widely used in sun care preparations: 1. safety non-toxic because it has following Some features; 2. ultraviolet screener efficiency is high; 3. suitable particle size range; 4. excellent dispersibility and the transparency; 5. good weatherability.But this series products is often moist not, and SPF (sun protection factor) is higher, larger to skin damage, easily causes xerosis cutis, aging.And, if the sun-proof granule size of this class is too large, do not there is transparency; Too little have a probability that enters pore injury health.Therefore, how reasonably, scientifically use TiO 2granule is one of focus of current cosmetic field.
Inorganic-organic core-shell composite has the Rigidity and strength of inorganic material and the advantageous property such as high tenacity, plasticity of organic material simultaneously, easily be cut into the material with special construction, so inorganic-organic core-shell composite has huge using value in fields such as optics, catalysis, microelectronics, biology and pharmacy simultaneously.
Hyaluronic acid (HA) is a kind of biopolymer acidic polysaccharose, and the disaccharidase unit being made up of D-Glucose aldehydic acid and N-acetyl-glucosamine forms.It is present in the position such as skin, skeleton.Its molecular energy carries 500 times of above moisture, is the best moisturizing composition of generally acknowledging at present, can make that skin is tender, smooth, wrinkle removing, increase elasticity, prevent aging, is widely used in recent years in maintenance skin care item.
Present inventor passes through TiO 2the assembling design of-HA gel core shell structure granules, with inorganic TiO 2granule is core, relies on the effects such as chemical bond, electrostatic force to make biomacromolecule HA at TiO 2surface forms " HA gel shell ", reaches effect of not only sun-proof but also moisturizing, and gel layer can also improve size, the transparency of granule, has improved its dispersion stabilization, thereby has completed the present invention.
Summary of the invention
An object of the present invention is to provide the core-shell structure particles of a kind of not only sun-proof but also Saccharideisomerate.
Another object of the present invention is to provide the preparation method of this core-shell structure particles.
A further object of the present invention is to provide the purposes of this core-shell structure particles at cosmetic field.
Core-shell structure particles provided by the invention is by the inorganic TiO of kernel 2granule and outer HA high-molecular gel form.
In granule of the present invention, the inorganic TiO of kernel 2granule is rutile titanium dioxide nano-particle.Described TiO 2granule is made up of chemical precipitation method.
In granule of the present invention, outer field natural HA high-molecular gel carries out cross-linking reaction by hyaluronic acid and forms.
In granule of the present invention, the inorganic TiO of kernel 2between granule and outer natural HA macromolecule, be connected by electrostatic interaction.
The present invention selects biopolymer HA, is because itself is with negative charge, with TiO positively charged after modification 2connect by electrostatic interaction, form TiO 2-HA nucleocapsid structure.
Outer macromolecule HA under the existence of cross-linking agent, molecule generation cross-linking reaction, the network-like gel stability encapsulated by structures of formation is at TiO 2the outside of granule.
The preparation method of core-shell structure particles provided by the invention comprises the following steps:
1) titanium sulfate solid is dissolved in deionized water, adds ammonia spirit, obtain white emulsion after stirring reaction, centrifugalize repeatedly, dries, and under the condition of 700-900 DEG C, after calcining, grinds to form white powder;
2) step 1) gained white powder is scattered in deionized water, adds silane coupler, fully centrifugalize after stirring ultrasonic dispersion, then vacuum drying, obtains modification TiO 2granule;
3) by step 2) gained modification TiO 2granule is dissolved in deionized water, regulates pH to 3-5, after abundant ultrasonic dispersion, join in the HA solution of pH5-6, more ultrasonic dispersion and mechanical agitation;
4) in step 3) gained mixed liquor, add cross-linking agent and catalyst, under room temperature, fully stir, reactant liquor is through dialysis postlyophilization.
In the step 1) of the inventive method, the time of calcining is preferably 30 minutes, and the white powder obtaining is inorganic nano TiO 2granule.
The step 2 of the inventive method) in adopt silane coupler be gamma-aminopropyl-triethoxy-silane (KH550).
The preferred 1-ethyl of cross-linking agent-(3-dimethylaminopropyl) the phosphinylidyne diimine (EDC) adopting in the step 4) of the inventive method, catalyst optimization citric acid.
In method of the present invention, the molecule of HA measures 3.5 × 10 3g/moL-1.2 × 10 6g/moL, is preferably 3.6 × 10 3/ moL-1.17 × 10 6g/moL.
In method of the present invention, EDC adds and measures 2-8ml, is preferably 2-6ml.
In a preferred version, the preparation method of the sun-proof granule of nucleocapsid structure of the present invention comprises the following steps:
1) chemical precipitation method is prepared TiO 2granule
The titanium sulfate solid that takes 4-10g, is dissolved in deionized water, adds 8-12ml ammonia spirit, stirring reaction 30min, and the white emulsion centrifugalize obtaining 5 times, dries, and at the temperature lower calcination 30min of 700-900 DEG C, grinds and forms white powder.
2) TiO 2granule modified
Take 0.1-0.5g TiO 2, be dissolved in 30ml deionized water, adding mass percent is the silane coupler of 10-30%, stirs 2h, ultrasonic 2h, centrifugalize, vacuum drying.
3) HA's is coated
Getting HA(molecular weight is 3.5 × 10 3g/moL-1.2 × 10 6g/moL) soluble in water, gained concentration is 1-5mg/ml.Get modification TiO 2soluble in water, concentration is 1-5mg/ml, and ultrasonic 1h takes out 2-5ml solution and joins in the HA solution of 30-50mL, ultrasonic 1h, and mechanical agitation 4h, spends the night.
4) shell HA gel is synthetic
Take out 25-30ml 3) TiO of gained 2-HA mixed liquor, adds 2-10ml cross-linking agent, and accounts for the catalyst of liquor capacity 1/20, and stirring reaction 10h at ambient temperature dialyses 2 days, lyophilization.
The present invention is with inorganic TiO 2granule is core, by the modification of silane coupler, its particle surface is become positively charged, and makes electronegative natural biological macromolecule HA be coated on its surface by electrostatic interaction, then, under cross-linking agent exists, in shell generation cross-linking reaction, forms gel.This core-shell configuration granule not only can have good sun-proof result, has good biocompatibility, moisture retention simultaneously.
The present invention is first at inorganic TiO 2particle surface modified biological high-molecular gel layer, has prepared the core-shell particle of existing sun-proof Saccharideisomerate again, and can improve the transparency of its solution, and this product can be applicable to the preparation of sunscreen cream, emulsion etc. in cosmetic field.
Brief description of drawings
Fig. 1 is the TiO that calcining obtains under 900 DEG C of conditions 2the XRD figure of granule.
Fig. 2, Fig. 3 are respectively TiO 2granule and TiO 2the infared spectrum of-HA core-shell structure particles.
Fig. 4, Fig. 5 are respectively TiO 2granule and TiO 2the TEM figure of-HA gel core shell structure granules.
Fig. 6 shows and leaves standstill TiO after 3 days 2and TiO 2the sedimentation situation of-HA.
Detailed description of the invention
For a more detailed description to the present invention with embodiment below.These embodiment are only the descriptions to best mode for carrying out the invention, scope of the present invention are not had to any restriction.
Embodiment 1
1. take 8g titanium sulfate solid, be dissolved in 100ml deionized water, add 10mL ammonia spirit, stirring reaction 30min, the white emulsion centrifugalize obtaining 5 times, dries, and at the temperature lower calcination 30min of 900 DEG C, grinds and obtains white powder.
2. take the TiO of 0.5g 2powder, is dissolved in 30ml deionized water, adds 212 μ L Silane coupling agent KH550s, stirs 2h, ultrasonic 2h, centrifugalize, vacuum drying.
3. (HA, molecular weight is 1.1 × 10 to get hyaluronic acid 4g moL -1) soluble in water, the concentration of sample is 5mg/mL, regulates pH to 5.Get modification TiO 2soluble in water, sample concentration is 2mg/mL, regulates pH to 4, takes out 5ml solution and joins in 50mL HA solution, ultrasonic dispersion 1h, mechanical agitation 4h after ultrasonic dispersion 1h.
4. take out the TiO of gained in 25ml step 3 2-HA mixed liquor, adds 2-8mL cross-linking agent 5wt%EDC, and 1.65mL catalyst (citric acid of 1wt%), and stirring reaction 10h under 25 DEG C of conditions dialyses 2 days, lyophilization.
The product that different cross-linking agent additions are obtained carries out ultraviolet-visible light transmission measurement, obtains table 1.
Visible, the ultraviolet transmission rate (granule density 0.02g/100mL) of the core-shell structure particles of the different EDC additions of table 1
Embodiment 2
1. take 8g titanium sulfate solid, be dissolved in 100mL deionized water, add 10mL ammonia spirit, stirring reaction 30min, the white emulsion centrifugalize obtaining 5 times, dries, and at the temperature lower calcination 30min of 900 DEG C, grinds to form white powder.
2. take the modification TiO of 0.5g 2powder, is dissolved in the deionized water of 30mL, adds 212 μ L Silane coupling agent KH550s, stirs 2h, ultrasonic 2h, centrifugalize, vacuum drying.
3. the HA that gets various molecular weight is soluble in water, and the concentration of sample is 5mg/mL, regulates pH to 5, gets modification TiO 2soluble in water, sample concentration is 2mg/mL, and ultrasonic dispersion 1h takes out 5mL solution and joins in 35mL HA solution, ultrasonic 1h, mechanical agitation 4h.
4. take out the TiO of gained in 25mL step 3 2-HA mixed liquor, adds 5mL cross-linking agent 5wt%EDC, and the citric acid of 1.5mL catalyst 1wt%, and stirring reaction 10h under 25 DEG C of conditions dialyses 2 days, lyophilization.
Different molecular weight HA is reacted to the product obtaining and carry out ultraviolet-visible light transmission measurement, the results are shown in Table 2.
Table 2 TiO 2visible, ultraviolet transmission rate (granule density 0.02g/100ml) after particle surface different molecular weight HA is crosslinked
Embodiment 3. is to TiO 2granule and TiO 2the characteristic spectrum of-HA core-shell structure particles and stability study
1. detect the TiO that under 900 DEG C of conditions, calcining obtains 2the XRD figure (Fig. 1) of granule, with rutile TiO 2collection of illustrative plates is consistent, shows prepared inorganic TiO 2granule is rutile-type.
2. utilize infared spectrum to analyze TiO 2the variation of granule modified front and back characteristic peak.Fig. 2, Fig. 3 are respectively TiO 2granule and TiO 2the infared spectrum of-HA core-shell structure particles.At 1700cm -1and 2925cm -1near there is respectively carbonyl (C=O) and methylene (CH 2) stretching vibration characteristic peak, and at 1700cm -1the stretching vibration peak that place occurs is the stretching vibration characteristic peak of carbonyl (C=O) in the ester bond that generates of HA cross-linking reaction, and in whole cross-linking reaction process, methylene (CH 2) be constant, definition peak area ratio A 1700/ A 2925value as the degree of cross linking, represent the cross-linking reaction degree of carrying out, in figure, from the bottom to top, HA molecular weight increases.
3. as seen from Table 1, along with the increase of the degree of cross linking, the ultraviolet section screen effect of the core-shell structure particles obtaining is constant, and visible ray section transmittance values increases gradually.
4. as seen from Table 2, along with participating in the increase of the HA molecular weight reacting, grain diameter increases gradually, and visible ray section transmittance values reduces, ultraviolet section transmittance values increases, and the sample transparency obtaining when the sample obtaining when HA molecular weight is described is larger than HA molecular weight is higher.
5. Fig. 4, Fig. 5 are respectively TiO 2granule and TiO 2the TEM figure of-HA gel core shell structure granules.TiO as seen from Figure 4 2granule is graininess, finds TiO from Fig. 5 2particle surface has been coated thin film, should be dry HA gel layer.
6. Fig. 6 shows and leaves standstill TiO after 3 days 2and TiO 2the sedimentation situation of-HA.Leave standstill after 3 days TiO 2solution upper strata becomes clarification, and a large amount of precipitations are arranged at bottom, and TiO 2it is translucent that-HA particle solution still keeps, and shown to be coated the TiO of HA gel 2the dispersion stabilization of-HA granule is better.
Core-shell configuration granule of the present invention, in not changing UV sun-proof result, has increased particle diameter widely, has improved granule dispersion stabilization, has biocompatibility and moisture retention simultaneously.

Claims (8)

1. a core-shell structure particles for existing sun-proof Saccharideisomerate again, by the inorganic TiO of kernel 2granule and outer HA high-molecular gel form, wherein said TiO 2granule is rutile titanium dioxide nano-particle, is made up of following steps: 1) titanium sulfate solid is dissolved in deionized water, adds ammonia spirit, after stirring reaction, obtain white emulsion, centrifugalize repeatedly, dries, and under the condition of 700-900 DEG C, after calcining, grinds to form white powder; 2) by step 1) gained white powder is scattered in deionized water, adds silane coupler, fully stir and ultrasonic dispersion after centrifugalize, then vacuum drying, obtains modification TiO 2granule.
2. core-shell structure particles as claimed in claim 1, wherein said HA high-molecular gel carries out cross-linking reaction by hyaluronic acid and forms.
3. the preparation method of core-shell structure particles described in claim 1 or 2, comprises the following steps:
1) titanium sulfate solid is dissolved in deionized water, adds ammonia spirit, obtain white emulsion after stirring reaction, centrifugalize repeatedly, dries, and under the condition of 700-900 DEG C, after calcining, grinds to form white powder;
2) by step 1) gained white powder is scattered in deionized water, adds silane coupler, fully stir and ultrasonic dispersion after centrifugalize, then vacuum drying, obtains modification TiO 2granule;
3) by step 2) gained modification TiO 2granule is dissolved in deionized water, regulates pH to 3-5, after abundant ultrasonic dispersion, join in HA solution, more ultrasonic dispersion and mechanical agitation;
4) in step 3) add cross-linking agent and catalyst in gained mixed liquor, under room temperature, fully stir, reactant liquor is through dialysis postlyophilization.
4. preparation method as claimed in claim 3, the time of wherein said calcining is 30 minutes.
5. preparation method as claimed in claim 3, wherein said silane coupler is KH550.
6. preparation method as claimed in claim 3, wherein said cross-linking agent is 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine.
7. preparation method as claimed in claim 3, wherein said catalyst is citric acid.
Described in claim 1 or 2 core-shell structure particles in the purposes of preparing in cosmetic product.
CN201310046158.8A 2013-02-05 2013-02-05 Sunscreening granule with TiO2-HA core-shell structure as well as preparation method and application thereof Expired - Fee Related CN103110535B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310046158.8A CN103110535B (en) 2013-02-05 2013-02-05 Sunscreening granule with TiO2-HA core-shell structure as well as preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310046158.8A CN103110535B (en) 2013-02-05 2013-02-05 Sunscreening granule with TiO2-HA core-shell structure as well as preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN103110535A CN103110535A (en) 2013-05-22
CN103110535B true CN103110535B (en) 2014-11-12

Family

ID=48408933

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310046158.8A Expired - Fee Related CN103110535B (en) 2013-02-05 2013-02-05 Sunscreening granule with TiO2-HA core-shell structure as well as preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN103110535B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108524309B (en) * 2018-07-17 2021-04-09 如薇化妆品有限公司 Sunscreen cosmetic with water resistance and preparation method thereof
CN110862560A (en) * 2019-11-11 2020-03-06 山东安华生物医药股份有限公司 Preparation method of crosslinked hyaluronic acid dry powder
CN112058260B (en) * 2020-09-19 2023-04-11 西安瑞特三维科技有限公司 Preparation of core-shell structure Ag/TiO at normal temperature 2 Method for preparing nanoparticles and application thereof
CN114515249A (en) * 2021-12-29 2022-05-20 河北麦森钛白粉有限公司 Preparation method of antibacterial powder with different colors under illumination
CN116617098B (en) * 2023-07-24 2023-10-24 广东药科大学 Modified hyaluronic acid-based moisturizing sun-proof composite material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101757689A (en) * 2010-01-19 2010-06-30 上海理工大学 Titanium or titanium alloy having TiO2-HA surface coating and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101757689A (en) * 2010-01-19 2010-06-30 上海理工大学 Titanium or titanium alloy having TiO2-HA surface coating and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
左雪芹.温敏性二氧化硅－透明质酸微凝胶的制备与表征.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2010, *

Also Published As

Publication number Publication date
CN103110535A (en) 2013-05-22

Similar Documents

Publication Publication Date Title
CN103110535B (en) Sunscreening granule with TiO2-HA core-shell structure as well as preparation method and application thereof
Fu et al. Construction of cellulose based ZnO nanocomposite films with antibacterial properties through one-step coagulation
Liu et al. Enhanced dispersion stability and heavy metal ion adsorption capability of oxidized starch nanoparticles
Zhang et al. Preparation and characterization of novel functionalized prochloraz microcapsules using silica–alginate–elements as controlled release carrier materials
CN106633967B (en) A kind of titanium dioxide/lignin-base composite nanometer particle and preparation method and application
Awan et al. Cellulose nanocrystal–ZnO nanohybrids for controlling photocatalytic activity and UV protection in cosmetic formulation
Arularasu et al. Synthesis and characterization of cellulose/TiO2 nanocomposite: Evaluation of in vitro antibacterial and in silico molecular docking studies
KR101557973B1 (en) Polymer Nano Particle Containing UV Blocking Material and Method for Preparing the Same
CN103304733B (en) A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel
CN103525405B (en) Magnetic fluorescent difunctional nano material based on natural polymer and preparation method thereof
CN104592702A (en) Self-healing organic matter/inorganic nanoparticle hybrid material and preparation method thereof
CN104741137A (en) Preparation method of titanium dioxide and doped body of titanium dioxide
CN107632002B (en) Composite fluorescent biosensor and preparation method and application thereof
CN113751079B (en) Perovskite-titanium dioxide nano composite photocatalyst loaded by biological material and construction method and application thereof
Zhang et al. Study on Photocatalytic Antibacterial and Sustained-Release Properties of Cellulose/TiO 2/β-CD Composite Hydrogel
CN103525805B (en) A kind of reproducible magnetic immobilized zymophore and preparation method thereof
Huang et al. Biopolymer as stabilizer and adhesive to in situ precipitate CuS nanocrystals on cellulose nanofibers for preparing multifunctional composite papers
CN113440423A (en) Modified titanium dioxide particle, preparation method thereof and skin care product
CN107338640A (en) A kind of polyester cotton fabric rare earth multifunctional composite finishing agent and preparation method thereof
Ivanuša et al. Eco-friendly approach to produce durable multifunctional cotton fibres using TiO2, ZnO and Ag NPs
KR20140080467A (en) Polymer Nano Particle Containing UV Blocking Material and Method of Preparing the Same
CN1296041A (en) Process for preparing nanometer zinc oxide
CN103849376A (en) Method of preparing porphyrin nanogold composite material with core-shell structure
CN100543072C (en) Ordered chitose crosslinked membrane and preparation method thereof
CN102774874B (en) Novel preparation method of nano-zinc oxide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20141112

Termination date: 20150205

EXPY Termination of patent right or utility model