CN1125147C - Modified nm zinc oxide UV ray shielding and absorbing material - Google Patents
Modified nm zinc oxide UV ray shielding and absorbing material Download PDFInfo
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- CN1125147C CN1125147C CN00114050A CN00114050A CN1125147C CN 1125147 C CN1125147 C CN 1125147C CN 00114050 A CN00114050 A CN 00114050A CN 00114050 A CN00114050 A CN 00114050A CN 1125147 C CN1125147 C CN 1125147C
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Abstract
The present invention relates to an ultraviolet screening/absorbing material of modified nanometer zinc oxide, which is prepared by an ultrasonic microemulsion method, and is formed by coating a non-ionic surface active agent on the surface of the nanometer zinc oxide or the nanometer zinc oxide with doped magnesium oxide for modification. The ultraviolet screening/absorbing range of the nanometer zinc oxide is expanded; the ultraviolet screening/absorbing material has high thermal stability, high chemical stability, no color, no poison, no abnormal odor and solvent resistance; in addition, the ultraviolet screening/absorbing material has good compatibility with various other base materials, and the ultraviolet screening/absorbing material has a good application prospect in the fields requiring ultraviolet screening, such as cosmetic, etc.
Description
The present invention relates to the modified nm zinc oxide UV ray shielding/absorbing material.
Ultraviolet screener/absorption agent is a kind of of photostabilizer, itself has excellent light stability, can absorb or flash back the sunlight and ultraviolet and fluorescence light source in ultraviolet part, own intensified and emit and do not have destructive longwave optical, phosphorescence or fluorescence when absorbing the ultraviolet ray back.The autoxidation reaction activity of most of polymkeric substance is 10～40 kcal/mol, and various chemical bond dissociation energies are 32～110.6 kcal/mol.Photon energy is 95 kcal/mol when wavelength is 95 kcal/mol during for 350nm during 300nm, during 200nm more up to 143 kcal/mol.Synthesize and natural macromolecular material, the skin that comprises human body, under irradiation under daylight and the UV-light, because of ultraviolet strong effect, cause the destruction of autoxidation reaction and chemical bond, the degraded that causes polymkeric substance is with aging, its outward appearance and mechanical property are degenerated, make us the blackening of body skin, burn, even cause and human body is damaged cancer.After adding ultraviolet screener/absorption agent, optionally shielding, uv reflectance, or after absorbing high-octane ultraviolet ray make it to become harmless longwave optical and discharge or consume, thereby can comprehensively protect human body and polymer materials.According to chemical property and structure, commercially available UV light absorber can be divided into following all kinds of: (one) para-amino benzoic acid ester and derivative thereof, (2) salicylate and derivative thereof, (3) cinnamate derivative, (4) hexichol (first) ketone compounds, (5) cinnamyl o-aminobenzoate, (6) diphenylpropane-1,3-dione(DPPO) compounds, (7) camphor analog derivative, (8) benzotriazole compound, (nine) macromole hindered amine, (ten) metal organic chelate, (11) some inorganic ultraviolet screener/absorption agent, for example carbon black of nanometer and submicron order, titanium oxide, zinc oxide, cerium oxide, stannic oxide, chromic oxide and cobalt oxide etc.The general addition of this series products of micron, submicron order is bigger, only is applicable to opaque goods.Nano-scale oxide ultraviolet screener/absorption goods, transparency is good, can not produce the opaque and outward appearance of turning white of powder, ultraviolet protection effect to 200～400nm is fine, has unreactiveness, and is safe in utilization, compare with the UV light absorber of mineral-type, organic class all be lower than mineral-type aspect thermostability, the solvent resistance, and great majority have certain toxicity, so each state is all in exploitation low toxicity, efficient, inexpensive UV light absorber.At present most widely used is the titanium oxide and the zinc oxide of nanometer and submicron order, nano level titanium oxide has strong absorption in 200～380nm wavelength band, and nano level zinc oxide only has stronger absorption (" cosmetic chemistry and the Technology complete works " first volume P618～bright firm work of 620 China Light Industry Press's fur coats) in 300～380nm wavelength band, though therefore more expensive having obtained of the price of titanium oxide used widely.
The purpose of this invention is to provide modified nano zinc oxide, change the wavelength region of its ultraviolet shielded/absorption, improve its uv-absorbing ability greatly.This uv-absorbing agent not only can shield/absorb ultraviolet ray consumingly, and thermostability, chemical stability height, colourless, nontoxic, odorless, anti-solvent, and good with various base material compatibilities, only need to add the requirement that less dosage just can reach ultraviolet screener/absorption.
Find to have in the nano zine oxide particulate of specific size and distribution thereof or the nano zine oxide and mix up zinc oxide/magnesium oxide particle that a certain amount of magnesium oxide forms by the X diffraction, the wavelength region of ultraviolet screener/absorption is compared with simple zinc oxide change has been taken place; Simultaneously from infrared absorption spectrum and ultra-violet absorption spectrum as can be seen, the surface coats the uv-absorbing scope that different tensio-active agents also can change nano zine oxide.
Modified nano zinc oxide particulate provided by the invention is to adopt nonionogenic tenside polyoxyethylene glycol (polymerization degree DP 〉=200) or sorbitan monooleate to be distributed in the mixed solvent that volume ratio is 1: 1～1.5 hexanaphthene and N-BUTYL ACETATE as microreactor, under ultrasonication, reactant (1mol/l) zinc acetate and pH=8～13 alkali lye (ammoniacal liquor or sodium hydroxide) are joined respectively in the mixed solution of above-mentioned mixed solvent and tensio-active agent and disperse to form microemulsion, mix making it reaction then, can obtain surfactant-modified nano zine oxide.(both mol ratios are 1～2: 1), can obtain magnesium oxide modified nano zine oxide to add certain magnesium acetate by method of the same race in zinc acetate solution.
A kind of modified nm zinc oxide UV ray shielding/absorbing material provided by the invention, adopt ultrasonic microemulsion method preparation, through tensio-active agent the nano zine oxide surface modification is formed, be coated with nonionogenic tenside polyoxyethylene glycol (polymerization degree DP 〉=200) or sorbitan monooleate on the surface of nano zine oxide, its median size is 40～250nm, in ultraviolet ray 220～400nm scope, strong absorption is arranged, its thermostability, chemical stability height, colourless, nontoxic, odorless, anti-solvent.
Particle diameter and uv-absorbing rate through Japanese JEM1010 transmission electron microscope and twin-beam UV-VI spectrometer mensuration nano material, only need to find this nano material of 40～250nm of the less dosage of admixture in hexanaphthene, uv-absorbing just can reach more than 89%, absorption region expansion simultaneously.And the wave band of the ultraviolet radiation absorption/shielding of this material distributes with its size and different-grain diameter, the kind of tensio-active agent is relevant.Its contrast situation with the nano zine oxide of no modification is as follows:
| Numbering | Tensio-active agent | Particle diameter (nm) | Uv-absorbing scope (nm) | Volumetric concentration in hexanaphthene (%) | Specific absorption (%) |
| 0 | No modification | 4～15 | 300～380 | Mass percentage concentration 5% in grease | 85 |
| 1 | Sorbitan monooleate | 40～70 | 220～280 | 0.8 | 96 |
| 2 | Polyoxyethylene glycol-400 | 100～250 | 250～300 330～400 | 0.8 | 90 |
| 3 | Polyoxyethylene glycol-200 | 100～200 | 250～290 | 0.8 | 89 |
Another kind of modified nm zinc oxide UV ray shielding/absorbing material provided by the invention, adopt ultrasonic microemulsion method preparation, form by nano zine oxide/magnesium oxide and nonionogenic tenside, in the lattice of zinc oxide, introduce magnesium oxide, its surface is coated with nonionogenic tenside polyoxyethylene glycol (polymerization degree DP 〉=200) or sorbitan monooleate, nano zine oxide and magnesium oxide mol ratio are 1～2: 1, its median size is 20～200nm, in ultraviolet ray 200～330nm scope, strong absorption is arranged, its thermostability, the chemical stability height, colourless, nontoxic, odorless, anti-solvent.
Particle diameter and uv-absorbing rate through Japanese JEM1010 transmission electron microscope and twin-beam UV-VI spectrometer mensuration nano material, only need to find this nano zine oxide/magnesium oxide composite material of the less dosage of admixture in hexanaphthene, uv-absorbing just can reach more than 95%, with do not mix up magnesian nano zine oxide under the similarity condition and compare, particle diameter reduces 10～50nm, and the ultraviolet radiation absorption range expansion is to blue shift 10～70nm.The wave band of the ultraviolet radiation absorption/shielding of this material changes with the kind of magnesian amount of mixing up and tensio-active agent.It is with simple as follows by the contrast situation of surfactant-modified nano zine oxide:
| Numbering | Form (mol ratio) | Tensio-active agent | Particle diameter (nm) | Uv-absorbing scope (nm) | Volumetric concentration in hexanaphthene (%) | Specific absorption (%) |
| 1 | Zinc oxide/magnesium oxide=1: 1 | Sorbitan monooleate | 30～60 | 200～290 | 0.8 | 98 |
| 2 | Zinc oxide | Sorbitan monooleate | 40～70 | 220～280 | 0.8 | 96 |
| 3 | Zinc oxide/magnesium oxide=2: 1 | Polyoxyethylene glycol-400 | 80～200 | 220～330 | 0.8 | 95 |
| 4 | Zinc oxide | Polyoxyethylene glycol-400 | 100～250 | 250～300， 330～400 | 0.8 | 90 |
Modified nano zinc oxide of the present invention has been widened its ultraviolet screener/absorption region, absorptive character also have raising, simultaneously the existence of tensio-active agent can make it good with various base material compatibilities, needs the field of ultraviolet screener to have a good application prospect at makeup etc.
Embodiment 1
Sodium hydroxide solution 0.8-1mL for 11-13 joins respectively in (the 7.0-12g/L sorbitan monooleate of 3.0-4.0ml)/(hexanaphthene of the 10-15ml) mixing solutions with the 0.5-1mol/L zinc acetate solution of 0.2-0.5ml and pH value, disperse at 32 ℃ of following ultrasonic oscillations, resulting zinc acetate and sodium hydroxide microemulsion are mixed, continue reaction in the ultrasonic oscillation condition, make the microemulsion that contains zinc oxide nano-particle, the diameter range of its nanoparticle is 40～70nm, ultraviolet radiation absorption scope 220～280nm.When nanoparticle content reached volume percent 0.8%, ultraviolet screener/specific absorption reached about 96%.
Embodiment 2
Ammoniacal liquor/ammonium chloride solution 0.1-0.5mL for 8-13 joins respectively in (0.2-0.6mL polyoxyethylene glycol-400)/(4-16mL N-BUTYL ACETATE)/(4-16mL hexanaphthene) mixing solutions with the 1mol/L zinc acetate of 0.1-0.5mL and pH value, constant temperature in 37-46 ℃, under the ultrasonic wave effect, disperse to form microemulsion, two microemulsion systems are mixed, continuation is reacted in ultrasonic wave, obtain the microemulsion of zinc oxide nano-particle, its particle size range is 100～250nm, the ultraviolet radiation absorption scope is 250～300,330～400nm.When nanoparticle content reached volume percent 0.8%, ultraviolet screener/specific absorption reached 90%.
Embodiment 3
Ammoniacal liquor/ammonium chloride solution 0.05-0.25mL for 8-13 joins respectively in (0.2-0.6mL polyoxyethylene glycol-200)/(6-18mL N-BUTYL ACETATE)/(6-18mL hexanaphthene) mixing solutions with the 1mol/L zinc acetate of 0.1-0.5mL and pH value, constant temperature in 35-46 ℃, under the ultrasonic wave effect, disperse, after forming two microemulsion systems, two microemulsion systems are mixed, under 44 ℃, continuation is reacted in ultrasonic wave, obtain the microemulsion of zinc oxide nano-particle, its particle size range is 100～200nm, ultraviolet radiation absorption scope 250～290nm.When nanoparticle content reached volume percent 0.8%, ultraviolet screener/specific absorption reached 89%.
Embodiment 4
Sodium hydroxide solution 0.5-2.0ml for 8-13 joins respectively (in the sorbitan monooleate of the 15-18g/L of 0.2-1.0ml (W=10-18) and the hexanaphthene mixing solutions with 0.5-1mol/L zinc acetate/magnesium acetate (wherein the mol ratio of zinc and magnesium is 1: 1) of 0.2-0.8ml and pH value, at 25-28 ℃ of following ultra-sonic dispersion, form two microemulsion systems, then with its mixing, continue under the ultrasound condition in 25-28 ℃ of reaction, make the nano magnesia original position and mix up the modified nano zinc oxide particle, the particle size range of its nanoparticle is 30～60nm, ultraviolet radiation absorption scope 200～290nm.When the volume percent of nanoparticle in hexanaphthene reached 0.8%, ultraviolet screener/specific absorption reached about 98%.
Embodiment 5
1mol/L zinc acetate with 0.25-0.6mL, magnesium acetate (wherein the mol ratio of zinc and magnesium is 2: 1) and pH value join respectively in (0.2-0.6mL polyoxyethylene glycol-400)/(8-12mL N-BUTYL ACETATE)/(6-10mL hexanaphthene) mixing solutions for ammoniacal liquor/ammonium chloride solution 0.6-1.0mL of 8-12, constant temperature is in 46 ℃, under the ultrasonic wave effect, disperse, after forming two microemulsion systems, two microemulsion systems are mixed, under 44 ℃, continuation is reacted in ultrasonic wave, obtain the nano magnesia original position and mix up modified nano zinc oxide, its particle size range is 80～200nm, and the ultraviolet radiation absorption scope is 220～330nm.When nanoparticle when volume percent reaches 0.8% in hexanaphthene, ultraviolet screener/specific absorption reaches about 95%.
Claims (1)
1, a kind of modified nm zinc oxide UV ray shielding/absorbing material, adopt ultrasonic microemulsion method preparation, form by nano zine oxide/magnesium oxide and nonionogenic tenside, it is characterized in that: in the lattice of zinc oxide, introduce a certain amount of magnesium oxide, its surface is coated with the nonionogenic tenside polyoxyethylene glycol or the sorbitan monooleate of polymerization degree DP 〉=200, nano zine oxide and magnesium oxide mol ratio are 1～2: 1 in the lattice, its median size is 20～200nm, in ultraviolet ray 200～330nm scope, strong absorption is arranged, its thermostability, the chemical stability height, colourless, nontoxic, odorless, anti-solvent.
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| CN00114050A CN1125147C (en) | 2000-01-28 | 2000-01-28 | Modified nm zinc oxide UV ray shielding and absorbing material |
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| CN00114050A CN1125147C (en) | 2000-01-28 | 2000-01-28 | Modified nm zinc oxide UV ray shielding and absorbing material |
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| CN1125147C true CN1125147C (en) | 2003-10-22 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1315970C (en) * | 2004-07-30 | 2007-05-16 | 上海家化联合股份有限公司 | Material of Nano pyrophosphate for absorbing ultraviolet ray, preparation method and usage |
| CN106672910B (en) * | 2017-01-06 | 2019-04-05 | 江苏启弘新材料科技有限公司 | A kind of strong function nano powder preparation method for absorbing ultraviolet light |
| CN107265494B (en) * | 2017-06-06 | 2019-04-02 | 安徽锦华氧化锌有限公司 | A kind of modified nano zinc oxide |
| CN107383699A (en) * | 2017-08-30 | 2017-11-24 | 桐城市华猫软膜有限公司 | A kind of computer casing special plastic material and preparation method thereof |
| CN110317459B (en) * | 2019-07-04 | 2021-09-21 | 安徽星鑫化工科技有限公司 | Chlorinated paraffin ultraviolet absorbent |
| CN115778869A (en) * | 2022-11-10 | 2023-03-14 | 四川缇肤生物科技有限公司 | Skin care product containing supramolecular zinc oxide and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
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