CN101583691A - Antioxidant - Google Patents
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- CN101583691A CN101583691A CNA2007800491088A CN200780049108A CN101583691A CN 101583691 A CN101583691 A CN 101583691A CN A2007800491088 A CNA2007800491088 A CN A2007800491088A CN 200780049108 A CN200780049108 A CN 200780049108A CN 101583691 A CN101583691 A CN 101583691A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/18—Antioxidants, e.g. antiradicals
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P39/00—General protective or antinoxious agents
- A61P39/06—Free radical scavengers or antioxidants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
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Abstract
An antioxidant comprising as an active ingredient, a 12CaO7Al2O3 compound and/or a 12SrO7Al2O3 compound and a mixed crystal thereof, each of which contains a negative hydrogen ion (H<->) at a concentration of 1 x 10<18> cm<-3> or more.
Description
Technical field
The present invention relates to contain the antioxidant of hydrogeneous anionic inorganic powder.
Background technology
Known mineral compound (the 12CaO7Al that contains hydride ion
2O
3Compound, 12SrO7Al
2O
3Compound or with 12 ((1-x) CaOxSrO) 7Al
2O
3(0＜x＜1) forms the 12CaO7Al of expression
2O
3And 12SrO7Al
2O
3The mixed grain effect compound) (patent documentation 1:WO2003/089373 communique).Known these compounds can show in atmosphere at room temperature through continued to be converted into the function of electric conductor after the rayed by isolator.But, do not know that still these compounds have excellent antioxidant effect.
In vivo, antioxygenation is being used for bringing into play important function aspect the health maintenance.Common antioxidant (free-radical scavengers) provides an electronics to make asymmetric electronic stability paired to free radical.In this case, though antioxidant itself becomes free radical, this free radical is normally stable, and can be converted into the non-free radical class by all means.Compound with phenol skeleton, thiol group has anti-oxidant activity usually.Antioxidant is used as the antioxidant of food, grease etc., and then is applied in the pharmaceuticals.As naturally occurring antioxidant tocopherol (vitamin-E), sesamin phenol (being present in the siritch), trans-resveratrol (being present in the red wine), catechin (being present in the tealeaves) etc. are arranged.
In addition, used antioxidant, in coating, grease, food, plastics etc., utilized as additive as the defence agent of corresponding oxygenizement.
Patent documentation 1WO2003/089373 communique
No. the 3533648th, patent documentation 3 Japanese Patents
Summary of the invention
Novel antioxidant is provided.
Antioxidant and the application thereof of the powder of the mineral compound (the mixed grain effect compound of 12CaO7Al2O3 compound, 12SrO7Al2O3 compound or 12CaO7Al2O3 and 12SrO7Al2O3) that will contain hydride ion as effective constituent are provided.
The main composition of the present application is as described below.
(1) antioxidant, its mixed crystal that will contain the 12CaO7Al2O3 compound of hydride ion (H-) of the above concentration of 1 * 1018cm-3 and/or 12SrO7Al2O3 compound and these compounds is as effective constituent.
(2) external composition for skin, it contains (1) described antioxidant.
(3) cosmetic material, it contains (1) described antioxidant.
(4) whitening agent, it contains (1) described antioxidant.
(5) antioxidant is used in the plastics interpolation, and it contains (1) described antioxidant.
(6) antioxidant is used in the coating interpolation, and it contains (1) described antioxidant.
Novel antioxidant can be provided.
The mineral compound powder that contains hydride ion of the present invention is brought into play excellent function as antioxidant.The antioxidant that can be used as plastics, coating, cosmetic material, grease etc. uses.
Description of drawings
Fig. 1 represents by IR and SIMS method the hydride ion amount to be carried out quantitative results.
Fig. 2 represents to measure the result of the sample solution ESR collection of illustrative plates of pure water solvent.
Fig. 3 represents the radical scavenging activity of embodiment 3 Sample A-2～A-4.
Fig. 4 represents the radical scavenging activity of embodiment 3 sample B-2～B-4.
Fig. 5 represents that embodiment 4 uses the radical scavenging activity of the sample C-2～C-4 of solvent C.
Fig. 6 represents that embodiment 4 uses the radical scavenging activity of sample D-2～D-4 of solvent D.
Fig. 7 represents the removing ability from the hydroxyl radical free radical of rayed titanium dioxide that embodiment 10 measures by the ESR method of using sample B.
Embodiment
In the present invention as initial substance, can be pure 12CaO7Al2O3 compound (the following C12A7 that is designated as sometimes), as long as in treating processes, do not destroy the distinctive mayenite of C12A7 (Mayenite) type crystalline texture, also can be part or all having and the mixed crystal of the equal crystalline texture of C12A7 compound, sosoloid (following these materials slightly are called coordinator matter) of calcium and aluminium by other element substitution.
As the material that has with the equal crystalline texture of C12A7 compound, now known have a 12SrO7Al2O3, and the ratio of mixture of Ca and Sr can freely change.That is: also can be the mixed grain effect compound of 12CaO7Al2O3 and 12SrO7Al2O3.In addition, the anionic kind of initial stage inclusion, quantity do not produce big influence to the importing effect of hydride ion.And then form can be in powder, film, polycrystal, the monocrystalline any.
As the C12A7 of initial substance, the atom equivalence ratio that contains calcium (Ca) and aluminium (Al) by use is the raw material of 12: 14 ratios, in sintering temperature more than 1200 ℃ and be lower than and carry out solid state reaction under 1415 ℃ and synthesize.Representative raw material is the mixture of lime carbonate and aluminum oxide.
Can obtain monocrystalline by zone melting method (FZ method) with the C12A7 sintered compact that obtains in the solid state reaction as precursor.The cultivation of C12A7 monocrystalline, by with infrared rays optically focused on bar-shaped ceramic precursor, lift precursor rods simultaneously, the melting zone is moved, on the interface of melting zone-solidify portion, make the monocrystalline continuous growth.The present inventor discloses the C12A7 compound monocrystal that contains the high density active oxygen and the manufacture method of bubble-free C12A7 monocrystalline in patent documentation 3 (No. the 3533648th, Japanese Patent).
With initial substance C12A7 and equal material in the environment more than hydrogeneous 1000ppm, preferably in the ambient windstream more than the hydrogeneous 20 volume % of oxygen-free, moisture, more than 800 ℃, preferred more than 1000 ℃ and be lower than 1350 ℃, more preferably under about 1300 ℃ temperature, according to the form of initial substance, keep cooling off after several minutes to a few hours.In order to obtain ambient containing hydrogen, can in the container of can high temperature resistant heat treated material making as silica glass, tantalum, fill hydrogen, initial substance is enclosed wherein.At this moment, also the material that can generate hydrogen by chemical reaction together can be enclosed wherein, to replace filling hydrogen.Pure C12A7 fuses when being heated to more than 1350 ℃ in ambient containing hydrogen, loses crystalline texture.
Implement hydrogen concentration in the heat treated environment and be 1000ppm when following, the amount that imports the hydride ion in C12A7 and the equal material is below 1 * 1018cm-3, is difficult to obtain excellent antioxidant effect in vivo.In addition, when thermal treatment temp is low more, import the easy more hydroxyl ion (OH-) that is replaced into of hydrogen ion in C12A7 and the equal material, when being lower than 800 ℃, because the amount of hydride ion is lower than 1 * 1018cm-3, so be difficult to obtain excellent anti-oxidant function equally.
Speed of cooling can be put coldly for electric furnace common naturally, but is preferably quick cooling, and it is more than 1 * 1018cm-3 that thermal treatment temp can make the quantitative change of hydride ion by quick cooling when low.
Through this material of above pyroprocessing, if pure C12A7 be raw material then be water white transparency, if powder then is white in color.When utilizing the condition of hydrogen reducing strong, import electronics, be light green in the part of cage structure.At this moment,, under the situation of the amount that does not reduce hydride ion, electronics is disappeared, form transparent or white states by keeping about 10 minutes under the temperature between 300 ℃ to 450 ℃.
Contain hydride ion or imported the state of hydride ion, be meant the hydride ion inclusion in C12A7 crystalline cage structure space.The lattice parameter of known C12A7 crystalline unit cell is about 1.2nm, represents with the composition of [Ca24Al28O64] 4+.When the importing by hydride ion all compensated 4 positive charges of per unit lattice, the quantity of the hydride ion that the C12A7 crystallization contains predicted that per 1 cubic centimetre mostly is 2.3 * 1021 most.
The inorganic powder that contains hydride ion is as the excellent function of antioxidant performance.The antioxidant that can be used as plastics, coating or make up material, medicine, grease etc. uses.
Embodiment
To be processed into the polished plate of minute surface of thickness 300 μ m by the C12A7 monocrystalline that zone melting method (FZ) is made.With its in oxygen in 1350 ℃ of thermal treatments 6 hours (Sample A).Then in the mixed gas air-flow of 20% volume hydrogen-80% volume nitrogen, after 2 hours, in equivalent environment, cool off fast, in the C12A7 crystallization, import hydride ion (sample B) 1300 ℃ of maintenances.
Then, cool off after in air, being warming up to 800 ℃, or remove or make it to become hydroxyl (OH-) (sample C) hydride ion.Utilize the intensity of 3560cm-1 place infrared absorption to obtain hydroxyl concentration in each sample.In addition, by secondary ion mass spectrometry (SIMS) the total amount concentration of the hydrogen that contains in each sample is carried out quantitatively.
In Sample A, C, hydrogen has almost all formed hydroxyl as proton.In sample B, the hydrogen proton free also exists as hydride ion outward.Utilize the quantitative values of the infrared absorption of Sample A, C and SIMS to make the calibration curve of proton concentration, can infer the concentration that the hydride ion in the sample B thus.These method of calculation are shown in the 1st figure.Become that the hydrogen concentration of hydride ion is speculated as 2 * 1020cm-3 in the sample B.
With reference to Fig. 5, the C12A7 sintered compact of density about 80% is carried out thermal treatment with sample B the same terms, import hydride ion.Because be the condition identical with sample B, hydride ion concentration is speculated as 2 * 1020cm-3.It is that dispersion medium, alumina balls are the planetary type ball-milling of crushing medium that this sintered compact is implemented with ethanol, makes powder.The specific surface area of powder is speculated as about 2m2/g by the BET method.
The DPPH radical scavenging activity is measured
(1) preparation of DPPH solution
(1.1-phenylbenzene picryl phenylhydrazine (1,1 '-diphenyl-2-picrylhydrazyl) already make with the pure pharmaceutical worker of light) is dissolved in 100% ethanol, preparation 0.00394w/v% solution to make DPPH.
(2) preparation of sample solution
Make solvent with pure water, the 0.1w/v% dispersion liquid of the sample B of preparation among the preparation embodiment 1.Handle 5 minutes with after the agglutinator pulverizing with ultrasonic echography, use agitator stir about 1 hour.Because powder is easily sedimentation in pure water, thus with also to stir before DPPH solution will soon mix with agitator.Use the contrast of pure water as the sample solution of pure water solvent.
(3) mensuration of ESR collection of illustrative plates
(device ESR-JES-TE200:JEOL)
Resonant frequency: 9.43GHz, output: 4.0mW, magnetic field modulation: 100kHz, observation magnetic field: 338.5 ± 5mT, minute: 1min, modulation amplitude: 0.1mT, amplification factor: 500 (when DPPH radical and lipid peroxidation can be measured), answering time: 0.03sec.
In plate reader with in dull and stereotyped sample solution (with 0.1w/v% is benchmark, dilutes 1/2,1/4,1/10 respectively) the 100 μ l of DPPH solution 100 μ l and pure water solvent being mixed, with free radical reaction after about 2 minutes, mensuration ESR collection of illustrative plates.Measurement result as shown in Figure 2.
The sample solution of pure water solvent
(pure water) observed free radical and had peculiar collection of illustrative plates in the contrast.After mixing 0.1w/v% sample B dispersion liquid, the peak disappears, and can confirm to have removed free radical.For being the solution of 0.01w/v% (1/10 dilution), 0.025w/v% (1/4 dilution), 0.05w/v% (1/2 dilution) when also carrying out same mensuration with 0.1w/v% powder dispersion dilution, confirm that radical scavenging activity has the powder concentration dependency with pure water.Utilize following formula to obtain radical scavenging activity.
(formula 1) radical scavenging activity (%)=(1-beta/alpha) * 100
At this, the peak height of the ESR collection of illustrative plates of β=sample B dispersion liquid+DPPH solution
The peak height of the ESR collection of illustrative plates of α=contrast (pure water)+DPPH solution
(4) result
The radical scavenging activity of 0.05w/v%, 0.025w/v%, 0.01w/v% concentrations samples B dispersion liquid is 83%, 43%, 8%.Show that radical scavenging activity has linear concentration dependent.Confirm that in addition IC50 is 0.021w/v%.Can confirm the anti-oxidant energy (DPPH radical scavenging activity) of sample B according to this result.
Oxidation about lipid suppresses effect (utilizing the squalene of ESR, oleic anti-oxidant can the evaluation)
(1) solvent
Use squalene (this special liver oil system purity 99.5% oxygen-free chemoprevention of bank is ended agent), oleic acid (with the pure pharmaceutical worker's industry of light one-level).
(2) spin trapping agent preparation
Make spin trapping agent α-Phenyl-N-tert-butylnitrone (α-phenyl-N-4-butyl nitrone) (, make 400mM solution hereinafter referred to as α-PBN) be dissolved in three (caprylic/capric) glyceryl ester (utilizing ultrasonic wave).
(3) measure specimen preparation
(solution of α-PBN) according to the use level preparation of table 1, is made ESR and is measured sample to add the sample B of embodiment 1 and spin trapping agent in the solvent sample.The weight percent of the concentration of sample B for calculating with (sample B weight)/(weight of solvent) * 100.
Table 1
(4) ESR measures
To each sample irradiation UV-A ripple, the free-radical generating amount when making finish generation oxidation with ESR mensuration.The UV irradiation time is as shown in table 1.
Utilize following formula to obtain radical scavenging activity.A-2～A-4 as shown in Figure 3, B-2～B-4 is as shown in Figure 4.
(formula 2) radical scavenging activity (%)=(1-beta/alpha) * 100
β=sample B dispersion liquid (the peak height of the ESR collection of illustrative plates of A-2～A-4 or B-2～B-4)
The peak height of the ESR collection of illustrative plates of α=contrast (A-1 (when β is A-2～A-4) or B-1 (when β is B-2～B-4))
(5) result
Add the result of the powder (sample B of embodiment 1) of 5w/w%, 2.5w/w%, 1.25w/w% in squalene, radical scavenging activity is 55%, 35%, 15%.Depend on powder concentration, demonstrate significant antioxidant effect.Confirm that in addition IC50 is 4.2w/w%.Add the result of the powder (sample B of embodiment 1) of 5w/w%, 2.5w/w%, 1.25w/w% in oleic acid, radical scavenging activity is 50%, 41%, 33%.Depend on powder concentration, demonstrate significant antioxidant effect.Confirm that in addition IC50 is 4.9w/w%.
About the oxidation of lipid suppress effect (utilize ESR saturated fatty acid+unsaturated fatty acids (oleic acid,
Squalene) anti-oxidant can the evaluation)
Oleic acid+three (caprylic/capric) glyceryl ester
Squalene+three (caprylic/capric) glyceryl ester
(1) solvent preparation
Carry out the preparation that ESR measures sample, following 3 kinds of finishes are mixed and use.The solvent of preparation is as described below.
Solvent C a: c=5: 5 (weight ratio) solvent D b: c=5: 5 (weight ratios)
A squalene (with the superfine 99% antioxidant alpha-tocopherol 0.05% of the pure pharmaceutical worker's industry of light)
B oleic acid (with the pure pharmaceutical worker's industry of light one-level)
C three (caprylic/capric) glyceryl ester (Myritol 318, Cognis)
(2) measure the sample preparation
For solvent C, D, add sample B, the α-PBN of embodiment 1 according to the use level of table 2, make ESR and measure sample (C-1～C-4, D-1～D-4).The weight percent of the concentration of sample B for calculating with (sample B weight)/(weight of solvent) * 100.
Table 2
(3) ESR measures
To each sample irradiation UV-A ripple, the free-radical generating amount when making finish generation oxidation with ESR mensuration.The UV irradiation time is shown in above-mentioned table 2.
Utilize following formula to obtain radical scavenging activity, the sample C-2～C-4 that uses solvent C as shown in Figure 5, the sample D-2～D-4 that uses solvent D is as shown in Figure 6.
(formula 3) radical scavenging activity (%)=(1-beta/alpha) * 100
β=sample B dispersion liquid (the peak height of the ESR collection of illustrative plates of C-2～C-4 or D-2～D-4)
The peak height of the ESR collection of illustrative plates of α=contrast (C-1 (when β is C-2～C-4) or D-1 (when β is D-2～D-4))
(4) result
(squalene: the result of the sample B of the embodiment 1 of interpolation 2.0w/w%, 1.0w/w%, 0.5w/w% three (caprylic/capric) glyceryl ester=5: 5), radical scavenging activity is 40%, 27%, 9% in solvent C.Depend on powder concentration, demonstrate significant antioxidant effect.Confirm that in addition IC50 is 2.9w/w%.(oleic acid: add powder (sample B of the embodiment 1) result of 2.0w/w%, 1.0w/w%, 0.5w/w% three (caprylic/capric) glyceryl ester=5: 5), radical scavenging activity is 66%, 42%, 26% at solvent D.Depend on powder concentration, demonstrate significant antioxidant effect.Confirm that in addition IC50 is 1.2w/w%.
Use TG (three (caprylic/capric) glyceryl ester) to be diluted to respectively at 50% o'clock squalene, oleic acid, similarly to Example 3, squalene, free radical concentration dependent under the powder effect of sample B that oleic acid oxidation produced are eliminated.
The preparation of plastic grain
(quality %)
(1) ABS resin 96
(2) calcium stearate 1
(3) sample B 3 of embodiment 1
(method for making) 200 ℃ of extrusion processinges, makes particle with above-mentioned (1)～(3).
The preparation of liquid foundation
(quality %)
(1) sweet oil 2
(2) caprylin 7
(3) trimethyl silicane alcoxyl base silicon ester 1
(4) silicon-dioxide 6
(5) decamethylcyclopentaandoxane 15
(6) octamethylcyclotetrasiloxane 15
(7) pure water remainder amount
(8) 1,3 butylene glycol 4
(9) titanium dioxide 12.5
(10) mica 3
(11) sample B 1 of embodiment 1
(12) spices 0.1
(13) sanitas 0.1
(method for making)
Mentioned component (1), (2), (12) and (13) are mixed and heating for dissolving (A phase).Composition (7) and (8) are mixed and dissolving (B phase).To pulverize (C phase) behind composition (4), (9), (10) and (11) uniform mixing.(D phase) mixed in composition (3), (5) and (6).After A reached D mutually and mix mutually, add C and mix mutually, add above-mentioned B again and carry out emulsification mutually.
Embodiment 7
The preparation of sunscreen
(quality %)
(1) titanium dioxide fine particles 5
(2) zinc oxide fine particles 15
(3) cerium oxide 5
(4) sample B 1 of embodiment 1
(5) octamethylcyclotetrasiloxane 1
20 (5) amino modified polyethers polysiloxane
(6) PIVALIC ACID CRUDE (25) isooctadecanol ester 10
(7) behenyl alcohol 3
(8) Rizinsan K2 A2 0.1
(9) pure water remainder
(method for making) with above-mentioned (5)～(7) composition in 80 ℃ of heating for dissolving (A phase).Add composition (1)～(4) to A and mix (B phase) in mutually.Behind (8), (9) uniform mixing, add it to B and carry out emulsification in mutually and mix.
The preparation of powdery foundation cream
(quality %)
(1) silicon is handled mica 20
(2) silicon is handled talcum 22.4
(3) fluorine is handled titanium dioxide 10
(4) amino acid is handled sericite 25
(5) silicon is handled iron oxide yellow 5
(6) silicon is handled red iron oxide 2.5
(7) silicon is handled iron oxide black 0.1
(8) sample B 1 of embodiment 1
(9) methyl polysiloxane (100cst) 11
(10) oxysuccinic acid two isooctadecanol esters 3
(method for making) slowly adds well-mixed (9)～(10) after with Henschel mixer (Henschel mixer) (1)～(8) being stirred 5 minutes, pulverizes with hammer mill.Be pressed into then in the foundation cream dish.
The preparation of eye shadow
(quality %)
(1) silicon is handled mica 10
(2) silicon is handled talcum 19
(3) amino acid is handled titanium dioxide 7
(4) amino acid is handled sericite 10
(5) nylon powder 10
(6) Si powder 10
(7) fluorine is handled iron oxide yellow 5
(8) fluorine is handled red iron oxide 10
(9) silicon is handled ultramarine 3
(10) sample B 1 of embodiment 1
(11) methyl phenyl silicone 8
(12) the hexadecanol 2-ethylhexanoate 7
(method for making) slowly adds well-mixed (11)～(12) after with Henschel mixer (Henschel mixer) (1)～(10) being stirred 5 minutes, pulverizes with hammer mill.Be pressed into then in the foundation cream dish.
Utilize the removing ability of ESR method evaluation from the hydroxyl radical free radical of rayed titanium dioxide
During with the rayed anatase titanium dioxide below the wavelength 380nm, produce free radical by light-catalyzed reaction.Whether the sample B of preparation removes the free radical that produces by rayed titanium dioxide fine particles aqueous dispersions among the embodiment 1, and (ESR) estimates with spectrum.By (coexistence of 5-N-oxide compound (5,5-Dimethyl-1-Pyrroline-N-Oxide)) prolongs life-span of free radical and measures with spin trapping agent DMPO.
(test method)
Anatase titanium dioxide particulate (median size 180nm) dispersion liquid 0.5% (w/v) 20 μ L, sample solution 180 μ L, the 10mM DMPO aqueous solution 200 μ L are mixed (adding up to 400 μ L), passed through the extra-high-pressure mercury vapour lamp irradiation ultraviolet radiation 1 minute when stirring with agitator.To pack the solution of ESR into in the sample pool through the mixed dispersion liquid of uviolizing, measure the ESR collection of illustrative plates of DMPO-OH.
As sample solution, use ion exchanged water (contrast), sample B dispersion liquid.The sample B dispersion liquid is to be used for immediately after being dispersed in sample B in the water measuring.The concentration that makes the sample B dispersion liquid is 1.22% (w/v), 1.67% (w/v), 2.22% (w/v), 10% (w/v), and the concentration that makes the sample B in the mixed dispersion liquid is 0.5% (w/v), 0.75% (w/v), 1.0% (w/v), 4.5% (w/v).
Using appts EMX8/2.7 type (BurkerBiospin) when ESR measures.With self-tuning (Autotune) decision condition determination.
Obtain radical scavenging activity with following formula.
(formula 3) free radical scavenging activity (%)=(1-beta/alpha) * 100
Second peak height that begins from downfield in the ESR collection of illustrative plates of the mixed dispersion liquid after the uviolizing of β=when using the sample B dispersion liquid as sample solution.
Second peak height that begins from downfield in the ESR collection of illustrative plates of the mixed dispersion liquid after the uviolizing of α=when using ion exchanged water (contrast) as sample solution.
(result)
The concentration of the sample B in the mixed dispersion liquid finds no radical scavenging activity when being 0.5% (w/v), 0.75% (w/v), demonstrates 38% radical scavenging activity when being 1.0% (w/v), demonstrates 86% removing ability when being 4.5% (w/v).The result as shown in Figure 7.
The inorganic powder that contains hydride ion that the present invention relates to is as the excellent function of antioxidant performance.
In plastics, coating or the fields such as material, medicine part outer article of making up, can cooperate, use and as the corresponding any amount of the purpose of antioxidant.
Claims (6)
1. antioxidant, it will contain 1 * 10
18Cm
-3Hydride ion (the H of above concentration
-) 12CaO7Al
2O
3Compound and/or 12SrO7Al
2O
3The mixed crystal of compound and these compounds is as effective constituent.
2. external composition for skin, it contains the described antioxidant of claim 1.
3. make up and expect that it contains the described antioxidant of claim 1.
4. whitening agent, it contains the described antioxidant of claim 1.
5. antioxidant is used in the plastics interpolation, and it contains the described antioxidant of claim 1.
6. antioxidant is used in the coating interpolation, and it contains the described antioxidant of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007009423 | 2007-01-18 | ||
| JP009423/2007 | 2007-01-18 | ||
| PCT/JP2007/070803 WO2008087774A1 (en) | 2007-01-18 | 2007-10-25 | Antioxidant |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101528167A Division CN102697665A (en) | 2007-01-18 | 2007-10-25 | Antioxidant |
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| Publication Number | Publication Date |
|---|---|
| CN101583691A true CN101583691A (en) | 2009-11-18 |
| CN101583691B CN101583691B (en) | 2012-11-14 |
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| CN2012101528167A Pending CN102697665A (en) | 2007-01-18 | 2007-10-25 | Antioxidant |
| CN2007800491088A Expired - Fee Related CN101583691B (en) | 2007-01-18 | 2007-10-25 | Antioxidant |
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|---|---|---|---|
| CN2012101528167A Pending CN102697665A (en) | 2007-01-18 | 2007-10-25 | Antioxidant |
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| Country | Link |
|---|---|
| JP (1) | JP5213122B2 (en) |
| KR (1) | KR101410636B1 (en) |
| CN (2) | CN102697665A (en) |
| HK (1) | HK1132758A1 (en) |
| WO (1) | WO2008087774A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101547164B1 (en) * | 2006-11-30 | 2015-08-25 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Light-emitting element and light-emitting device employing the same |
| CN105170432A (en) * | 2015-10-13 | 2015-12-23 | 太仓市和准电子科技有限公司 | Hardware surface coloring and spraying technology |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102131735A (en) | 2008-08-27 | 2011-07-20 | 旭硝子株式会社 | Mayenite-type compound and process for production of same |
| CN102459082B (en) * | 2009-06-12 | 2014-08-06 | 株式会社芳珂 | 12CaO7Al2O3 compound |
| JP5983086B2 (en) * | 2012-06-26 | 2016-08-31 | 堺化学工業株式会社 | Cosmetics |
| CA2883503C (en) | 2012-09-20 | 2020-08-11 | Tokyo Institute Of Technology | Catalyst for producing hydrogen and method for producing hydrogen |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2722792B1 (en) * | 1994-07-21 | 1996-09-06 | Ceca Sa | COMPOSITIONS OF THE MIXED HYDROXIDE TYPE OF ALUMINUM AND ALKALINE EARTH AS ANTICHLORINE AND ANTI-ACID AGENTS FOR THE STABILIZATION OF THERMOPLASTIC RESINS |
| JP3531868B2 (en) * | 2000-04-18 | 2004-05-31 | 独立行政法人 科学技術振興機構 | 12CaO · 7Al2O3 compound that includes active oxygen species and method for producing the same |
| JP3533648B2 (en) * | 2001-07-26 | 2004-05-31 | 独立行政法人 科学技術振興機構 | Reactive oxygen species inclusion calcia-alumina oxide single crystal and method for producing the same |
| JP2003089373A (en) * | 2001-09-17 | 2003-03-25 | Toyoaki Hayashi | Burglar-proof device of baggage for two wheeler |
| AU2003227435A1 (en) * | 2002-04-19 | 2003-11-03 | Japan Science And Technology Corporation | Hydrogen-containing electrically conductive organic compound |
| JP2004026608A (en) | 2002-06-27 | 2004-01-29 | Japan Science & Technology Corp | Electrically conductive inorganic compound including alkali metal |
-
2007
- 2007-10-25 WO PCT/JP2007/070803 patent/WO2008087774A1/en active Application Filing
- 2007-10-25 KR KR1020097014312A patent/KR101410636B1/en not_active IP Right Cessation
- 2007-10-25 JP JP2008553958A patent/JP5213122B2/en not_active Expired - Fee Related
- 2007-10-25 CN CN2012101528167A patent/CN102697665A/en active Pending
- 2007-10-25 CN CN2007800491088A patent/CN101583691B/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101547164B1 (en) * | 2006-11-30 | 2015-08-25 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Light-emitting element and light-emitting device employing the same |
| CN105170432A (en) * | 2015-10-13 | 2015-12-23 | 太仓市和准电子科技有限公司 | Hardware surface coloring and spraying technology |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008087774A1 (en) | 2008-07-24 |
| CN102697665A (en) | 2012-10-03 |
| JPWO2008087774A1 (en) | 2010-05-06 |
| JP5213122B2 (en) | 2013-06-19 |
| KR101410636B1 (en) | 2014-06-20 |
| HK1132758A1 (en) | 2010-03-05 |
| KR20090109535A (en) | 2009-10-20 |
| CN101583691B (en) | 2012-11-14 |
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