KR20120031167A - 12CaO-7Al2O3 COMPOUND - Google Patents

Abstract

Surface treatment using phosphate and electrons (e ⁻ ) of 2 × 10 ¹⁸ cm ⁻³ or more and less than 2.3 × 10 ²¹ cm ⁻³ , in which the number of people is detected from the powder surface by an energy dispersive X-ray analyzer, by using 12CaO? 7Al ₂ O ₃ compound including, the number of the external preparation for skin, such as a make-up cosmetic suppress the dispersion represents an alkali.

Description

12CaO7Al2O3 compound {12CaO-7Al2O3 compound}

The present invention relates to an inorganic compound (12CaO-7Al ₂ O ₃ compound).

An inorganic compound containing an electron to the gap in the crystal structure (? 12CaO 7Al ₂ O ₃ compound) is known (Patent Document 1: WO2005 / Publication No. 741). It is known that this compound can express high electroconductive function in room temperature atmosphere. The manufacturing method of this compound is disclosed by patent document 2, for example. This inventor discovered that this compound has the outstanding antioxidant effect, and applied for a patent (Japanese Patent Application No. 2008-287781).

The present inventor tried to apply this compound to make-up cosmetics while continuing research and development, but when this compound was disperse | distributed to water, the liquid liquid of water became alkaline and the antioxidant capability was inactivated.

International Publication No. 2005/000741 pamphlet International Publication No. 2006/129674 pamphlet

It is an object of the present invention to develop a technique for suppressing the alkalinity when an inorganic compound (12 CaO ₇ Al ₂ O ₃ compound) is dispersed in water.

The main structure of this invention is as follows.

1. Electrons of 2 × 10 ¹⁸ cm ⁻³ or more and less than 2.3 × 10 ²¹ cm ⁻³ , surface treated using phosphate and detected by human energy from the surface of the powder by an energy dispersive X-ray analyzer (e ⁻ 12CaO-7Al ₂ O ₃ compound comprising a).

2. Electrons less than 1 × 10 ¹⁸ cm ^-3 or more and less than 2.3 × 10 ²¹ cm ^-3 , surface-treated with phosphate and detected by the energy dispersive X-ray analyzer from the surface of the powder (e ⁻ 12CaO-7Al ₂ O ₃ compound comprising a).

3. After surface treatment using phosphate suspends a 12CaO 7 Al ₂ O ₃ compound containing electrons (e ⁻ ) of 1 × 10 ¹⁸ cm ⁻³ or more and less than 2.3 × 10 ²¹ cm ^-3 in an aqueous solution of phosphate, It is the process of filter-separating and drying this compound powder, The compound as described in 1. characterized by the above-mentioned.

4. The compound according to 1. or 2., wherein the pH of the dispersion within 60 minutes immediately after dispersion in ion-exchanged water at a concentration of 0.5% by mass is 8 or less.

5. Infrared spectrum absorption is confirmed by 1100 ± 50 cm ^-1 . The compound as described in any one of them.

6. Antioxidant which uses the compound as described in any one of 1.-5. As an active ingredient.

7. The external preparation for skin containing the antioxidant according to 6.

The external preparation for skin which does not contain water containing the antioxidant described in 8. 6 ..

9. The external preparation for skin according to 7. or 8., wherein the external preparation for skin is a makeup cosmetic.

Antioxidant for plastic addition containing the compound as described in any one of 10. 1.-4, or the antioxidant as described in 6 ..

An antioxidant for paint addition containing the compound according to any one of 11. 1. to 5. or the antioxidant according to 6.

By carrying out phosphate treatment, when an inorganic compound (12CaO-7Al ₂ O ₃ compound) was dispersed or contacted with water, it was possible to provide a compound which exhibits neutral to acidic properties and can suppress alkaline manifestations.

Even after phosphate treatment, the electron concentration before the treatment is maintained to exhibit an antioxidant effect, and is suitable as an external preparation for skin and cosmetics.

Since discoloration is suppressed even when it contacts water, it is suitable as a compounding material of cosmetics. When used as a powder cosmetic or makeup cosmetic, it does not discolor even when it contacts moisture, such as sweat, and is suitable.

It is also suitable as an antioxidant to be incorporated into plastics and paints.

1 is a graph showing the infrared spectrum of a 3.7 M phosphate treated electride C12A7 compound.
FIG. 2 is a diagram showing an SEM photograph of a 3.7 M phosphate-treated electron hydrate C12A7 compound. FIG.
3 is a graph showing an energy dispersive X-ray (EDX) analysis spectrum of the 3.7 M phosphate-treated electron hydrate C12A7 compound.
4 is a graph showing changes over time of the pH of ion-exchanged water in which phosphate-treated electronic powder C12A7 compound powder is dispersed.
FIG. 5 is a graph showing the change over time of pH according to the concentration of the 0.85 M phosphate-treated electronic powder C12A7 compound powder.
Fig. 6 is a diagram showing the radical scavenging ability of the phosphate-treated electronide C12A7 compound.
FIG. 7 is a graph showing an infrared spectrum of a 5 M phosphate-treated electron hydrate C12A7 compound. FIG.
FIG. 8 is a graph showing changes over time of pH of ion-exchanged water in which the 5 M phosphate-treated electronic powder C12A7 compound powder is dispersed.
9 is a view showing the radical scavenging ability of the 5 M phosphate-treated electronide C12A7 compound.

In the present invention, the starting material may be a pure 12CaO-7Al ₂ O ₃ compound (hereinafter, may also be described as C12A7), and during treatment, the mayenite type crystal structure peculiar to C12A7 is destroyed. Unless otherwise mentioned, mixed crystals or solid solutions (hereinafter, abbreviated to these as equivalent materials) may have a crystal structure equivalent to a C12A7 compound in which part or all of calcium and aluminum are substituted with other elements.

A material having a crystal structure equivalent to the C12A7 compound present 12SrO? A 7Al ₂ O ₃ is known and can be freely changed the mixing ratio of Ca and Sr. That is, 12CaO? 7Al ₂ O ₃ and 12SrO? It may be a mixed crystal compound of 7Al ₂ O _3. In addition, the kind and quantity of anion enclosed initially do not have a big influence on the effect of withdrawing free oxygen and substitution with an electron. In addition, the form of starting material may be any of a powder, a film, a polycrystal, and a single crystal.

The starting material C12A7 is synthesized by solid phase reaction at a calcination temperature of not less than 1200 ° C and less than 1450 ° C using a raw material containing calcium (Ca) and aluminum (Al) in an atomic equivalent ratio of 12:14. Representative raw materials are mixtures of calcium carbonate and aluminum oxide.

A single crystal can be obtained by a high melting method (FZ method) using the C12A7 sintered compact obtained by solid-phase reaction as a precursor. In the growth of the C12A7 single crystal, the melting rod is moved by concentrating the precursor rod while focusing infrared rays on the rod-shaped ceramic precursor to continuously grow the single crystal at the interface of the melting zone and the solidification portion. The present inventors have disclosed in Japanese Patent No. 3533648 a method for producing a C12A7 compound single crystal containing a high concentration of active oxygen species and a bubble-free C12A7 single crystal.

The starting material C12A7 and the equivalent material are held at a temperature of 600 ° C. or higher and less than 800 ° C., preferably at a temperature of 700 ° C. for 4 hours to 240 hours in an atmosphere containing alkali metal or alkaline earth metal vapor, and then 300 Cool to room temperature at a rate of temperature drop of about ° C / hour. In the atmosphere containing alkali metal or alkaline earth metal vapor, the alkali metal piece or powder or alkaline earth metal piece, powder and starting material may be vacuum-sealed in a container having thermal and chemical durability such as quartz glass.

Alkali metal may be included in the single crystal of the C12A7 compound and the same type compound, and therefore, for the purpose of drawing out free oxygen, it is preferable to use alkaline earth metal vapor which is less likely to be included, and the starting material is a C12A7 compound. Most preferably, calcium metal vapor contained in the starting material is used. The alkali metal or alkaline earth metal vapor is deposited on the surface of the single crystal and reacts with the free oxygen contained in the single crystal to form, for example, a calcium oxide layer on the surface when calcium is used. When the temperature at which the single crystal is held and maintained is less than 600 ° C., particularly below 500 ° C., the extraction reaction of free oxygen is remarkably slow, and at 800 ° C. or more, the extraction of free oxygen proceeds rapidly, and the C12A7 compound and the isoform are decomposed. Throw it away.

With the length of retention and retention time, the amount of free oxygen taken out increases, and the surface of the calcium oxide layer becomes thick. At 700 ° C., if retained and held for 240 hours, almost all of the free oxygen is taken out and replaced with electrons to form an electride C12A7 compound inside the calcium oxide layer. The amount of free oxygen extracted can be obtained from the X-ray diffraction spectrum, the thickness of the calcium oxide layer, the light absorption band intensity having a peak at 0.4 eV, and the electrical conductivity.

The fine powder of the starting material C12A7 compound and the same type compound is molded by uniaxial press, and then further molded by hydrostatic press. If the starting material is molded so that the hydrostatic press can be performed, the first uniaxial press may be omitted. The molding pressure of the uniaxial press is about 200 kg / cm 2 or more, about 400 kg / cm 2 or less, preferably about 300 kg / cm 2, and the molding pressure of the hydrostatic pressure press is preferably about 2000 kg / cm 2.

The obtained molded article is placed in a reducing atmosphere, preferably in a capped carbon crucible, and the crucible is placed in a capped alumina crucible to raise the temperature to 1550 ° C or more and less than 1650 ° C, preferably about 1600 ° C, and to the temperature. It cools after hold | maintaining and holding | maintaining for 1 minute or more and less than 2 hours, Preferably 1 hour. This temperature raising and lowering process is preferably repeated two or more times. When the holding and holding temperatures are higher than the above ranges, single-phase C12A7 compounds and isoforms cannot be produced. When the holding and holding temperature is less than 1550 ° C. and the holding and holding time is less than 1 hour, single-phase C12A7 compounds and isoforms can be produced, but free oxygen and electron substitution do not occur. When the retention time is less than 1 minute, only free oxygen of less than 1x10 ¹⁸ atoms / cm 3 is replaced with the electrons.

In addition, since the amount of substitution of free oxygen and electrons is substantially saturated within 2 hours, it is not necessary to hold or maintain for 2 hours or more. In addition, the temperature rise and the temperature lowering process is one of the more than 1550 ℃, less than 1650 ℃, also when its holding? Holding time is less than 1 hour, the product, 3CaO? Al ₂ O ₃ phase (C3A) or CaO? Al ₂ O _3, and the (CA), because these formed on the cage does not exist and can not access the e-port. However, by repeating the same temperature raising and lowering processes, the C12A7 compound and the same type compound containing electrons can be produced.

By pressure-molding a powder at such a pressure, it is thought that the speed | rate of a free oxygen withdrawal reaction is eased, and a C12A7 compound is obtained even after free oxygen withdrawal. When pre-oxygen extraction reaction is carried out in the state of fine powder without pressure molding, the product is decomposed into a 3CaO-Al ₂ O ₃ phase (C3A) or a CaO-Al ₂ O ₃ phase (CA), and cages do not exist in these phases. Because it does not, the former cannot be included.

The temperature increase rate is about 400 ℃ / hour. Temperature-fall rate is about 400 degreeC / hour, and it cools to room temperature. The temperature increase rate does not have a great influence on the product, and about 400 ° C / hour is easily obtained in a normal electric furnace. In order to significantly increase the temperature increase rate to 500 ° C / hour or more, a large electric furnace is required. If the temperature-fall rate is remarkably large at 500 ° C / hour or more, the obtained compound becomes glassy and difficult to crystallize. However, in the temperature increase process after the 2nd time, even if the temperature-fall rate is 500 degreeC / hour or more, it is easy to produce a C12A7 compound and an isoform compound.

Even if the carbon crucible is directly installed in an electric furnace, a product is obtained, but a carbon crucible may be installed in an alumina crucible to prevent contamination from the heater of the electric furnace and to alleviate the reaction of the carbon crucible with the atmosphere. . The obtained compound is black (powder is green), and it can be seen that it is C12A7 phase by X-ray diffraction. Moreover, the electrical conductivity of about 1 S / cm is shown and it can confirm that free oxygen ion is substituted by the electron.

The polycrystalline thin film of the C12A7 compound and the same type compound is obtained by forming and maintaining an amorphous film on a MgO substrate by pulse laser deposition method on a MgO substrate, and then holding it at about 1100 ° C. in the air.

The polycrystalline thin film of the C12A7 compound or the same type compound deposited on the MgO substrate was held at 600 ° C, and Ar ions accelerated to about 360 kV were embedded in the thin film. The thin film before ion implantation shows electrical insulation. An electrical conductivity of about 1 S / cm is obtained for a dose of 5 x 10 ¹⁷ / cm 2. From Rutherford backscattering spectra, it is confirmed that Ar ions are not contained in the film. Therefore, since the Ar ions collide with the free oxygen ions and the free oxygen ions are thrown out of the film by the knock-on effect and maintain electrical neutrality, it is considered that the electrons remain in the film.

In the case of the electronized C12A7 compound from which free oxygen has been removed, two electrons are left in the compound per oxygen ion in order to maintain electrical neutrality. Such free oxygen and the substituted electron are loosely bound in the cage, and can hop and move between cages. Since the amount of free oxygen is contained in the compound at about 1.1 × 10 ²¹ atoms / cm 3, the electron concentration is 2.3 × 10 ²¹ atoms / cm 3 when the total amount is replaced by electrons. Since the mobility of electrons at room temperature is about 0.1 cm 2 / (V sec), the electrical resistance is about 100 S / cm. In addition, loosely bound electrons in the cage result in two light absorption bands having peaks at 0.4 eV and 2.8 eV. For this reason, with the increase of the electron inclusion amount, a C12A7 compound is colored yellow, green, and black-green. In addition, the amount of electrons entrapped can be obtained from the intensity of these absorption bands.

Since the electrons contained in the C12A7 compound and the same type compound are loosely bound in the cage, they can be taken out by applying a high field from the outside at room temperature. That is, the C12A7 compound and the same type compound containing a large amount of electrons can be used as an electron emitting material. Electron emission occurs over a wide temperature range, resulting in currents as high as 10 μA even at room temperature.

In the present invention, 1 × 10 ¹⁸ ㎝ ^-3 or more, 2.3 × 10 ²¹ ㎝ ^-3 electron (e ^-) of less than are called 12CaO containing 7Al ₂ O ₃ compound e cargo C12A7 compound?. Electronized C12A7 compounds exhibit antioxidant activity in water or in water. However, the electronide C12A7 compound causes the problem of making the pH of water basic in water. In addition, the electronide C12A7 compound emits electrons in water, causing a problem of whitening and loss of antioxidant capacity.

Thus, by the following method, the electronized C12A7 compound is treated to improve stability.

The electronized C12A7 compound was suspended in the aqueous solution of phosphate, and the hydrated electronicized C12A7 compound was dried, and the stable surface of the phosphate-treated C12A7 compound was obtained.

As a phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, etc. are mentioned, for example. In addition, orthophosphoric acid and polyphosphoric acid equilibrate in phosphoric acid solution, You may use polyphosphate. Among the phosphates, sodium dihydrogen phosphate and potassium dihydrogen phosphate are preferable. In addition, the solution used for a process may be phosphoric acid itself.

As for the density | concentration of the aqueous solution of a phosphate, 0.1 M-saturated concentration (7 M in the case of aqueous sodium dihydrogen phosphate) are preferable, and 0.85 M-5 M are especially preferable. The higher the concentration of the phosphate aqueous solution, the higher the stability of the electronized C12A7 compound, and when the amount of water contacted by the electronized C12A7 compound is small, the surface-treated with a low concentration aqueous solution of phosphate exhibits stability.

It is preferable to stir the electronic compound C12A7 compound suspended in the phosphate aqueous solution using a stirrer, such as a magnetic stirrer. The stirring time is preferably about 1 to 30 minutes. In the case of treatment using an aqueous solution of the same concentration, the longer the stirring time is, the higher the effect of suppressing the increase in pH.

In the case of filtering and fractionating the electronized C12A7 compound suspended in the phosphate aqueous solution, suction filtration is preferable, and the filtered and separated electronized C12A7 compound is washed several times with a hydrophilic solvent such as ethanol and attached to the electronized C12A7 compound. The aqueous phosphate solution can be washed off. The clarified evaporated C12A7 compound can be dried by means such as vacuum drying.

The concentration of electrons (e ⁻ ) in the electronized C12A7 compound treated with an aqueous solution of sodium dihydrogen phosphate at a concentration of 0.85 M or higher was hardly reduced, and was maintained at 1 × 10 ¹⁸ cm ⁻³ or more and less than 2.3 × 10 ²¹ cm ^-3. do.

The phosphate-treated electronide C12A7 compound of the present invention has an excellent function as an antioxidant. It can be used as an antioxidant such as plastics, paints or cosmetics, medicine and fats and oils. In particular, by blending in powder foundation, powdered powder or oily makeup cosmetics, the effect of inhibiting the oxidation of the unsaturated bonds contained in sebum can be expected, and the effect of maintaining a good skin condition can be expected. Particularly, non-aqueous cosmetics are preferred for maintaining the stability of the phosphate-treated electronics C12A7 compound. Examples of the non-aqueous cosmetics include powder foundation, powdered powder, ointment foundation, solid foundation, lipstick, concealer, and the like.

Example 1

Preparation of Electrolyzed C12A7 Compounds

Heat-treatment that puts the fine powder of C12A7 compound produced by the large melting method (FZ method) into a carbon container with a lid and heats it to 1300 ° C. in a nitrogen flow furnace with a nitrogen gas atmosphere having an oxygen concentration of 10 vol. Ppm for 2 hours. Was performed. The obtained powder showed black green color.

After the obtained solid material was pulverized, the spin concentration (= electron concentration) was measured by X-Band ESR. CuSO _4? Was the 5H ₂ O in strength standards. As a result, the electron concentration of the obtained solid (electronized C12A7 compound) was 6.2 x 10 ¹⁸ cm ^-3 . In addition, it was confirmed from the powder X-ray diffraction that the obtained solid product was C12A7.

(Surface treatment)

Aqueous solutions of sodium dihydrogen phosphate at various concentrations shown in Table 1 were prepared.

0.5 g of the electronized C12A7 compound and 10 mL of an aqueous sodium dihydrogen phosphate solution were mixed and stirred for 10 minutes with a stirrer. The powder and the aqueous solution were separated by suction filtration, and ethanol was flowed several times to wash the aqueous solution adhering to the powder. The filter paper powder was vacuum dried to obtain a surface-treated powder. 0.85 M phosphate-treated electronized C12A7 compound surface-treated with aqueous solution of sodium dihydrogen phosphate No. 1, 3 M phosphate-treated electronized C12A7 compound surface-treated with aqueous solution of sodium dihydrogen phosphate No. 2 The hydrated C12A7 compound and the hydrated C12A7 compound surface-treated with No. 3 aqueous sodium dihydrogen phosphate solution are called 3.7 M phosphate-treated hydrated C12A7 compound.

(Measurement of Electron Concentration of Surface Treated Powder)

The spin concentration (= electron density) of the obtained phosphate-treated electronized C12A7 compound was measured by X-Band ESR. CuSO _4? A result of calculation by the 5H ₂ O to the reference sample, the electron concentration of each sample was as for Table 2. As shown in Table 2, even when phosphate treatment was performed, substantially no decrease in electron concentration occurred at the same level as the original electron concentration (6.2 × 10 ¹⁸ cm ⁻³ ).

(Infrared spectrum measurement of surface treated powder)

Infrared spectrometer during Fourier transformation manufactured by Perkin Elmer for each powder of untreated e-hydrate C12A7 compound, 3.7 M phosphate-treated e-hydrate C12A7 compound, NaH ₂ PO ₄ (anhydrous), Ca ₃ (PO ₄ ) ₂ Infrared spectrum was measured by ATR method.

As shown in the infrared spectrum shown in FIG. 1, the absorption spectrum of 1111 cm ⁻¹ was confirmed in the infrared spectrum (see the curve shown in FIG. 1A) of the 3.7 M phosphate-treated electronized C12A7 compound. Absorption of 1111 cm ^-1 was not confirmed (see the curve shown in FIG. 1B). This absorption is assumed to originate from the characteristic absorption of a phosphate group. The shape of the absorbent 1111 is ㎝ ^-1, is different from the infrared spectrum of the NaH ₂ PO ₄ (anhydrous). In addition, Ca ₃ (PO ₄₎ an infrared spectrum of the _second, there is the characteristic absorption of the phosphoric acid group 1020 ㎝ ^-1. By the surface treatment of the present invention, the metal and acid in the reaction C12A7 compound, possibly a phosphate, such as Ca ₃ (PO _{4) 2} is produced.

(Scanning Electron Microscopy and Energy Dispersive X-ray Analysis of Surface-treated Powders)

Surface-treated powders were observed using a scanning electron microscope (S-3400N manufactured by Hitachi High-Technologies Co., Ltd.), and energy concentration X-ray analyzer (EMAX ENERGY EX-350 manufactured by HORIBA) was used to measure the concentration of the surface-treated persons. Measured.

The process powder was apply | coated on the carbon tape, and the part which adhered and adhere | attached was made into the observation visual field.

EDX spectra of the entire observation field were measured at low vacuum observation (30 Pa), magnification 3000 times, acceleration voltage 15 kV, probe current 60, process time 5, and live time 180 seconds.

As a result of the EDX analysis, the presence of carbon, oxygen, sodium, aluminum, phosphorus and calcium was confirmed. Except for the carbon derived from the carbon tape, the concentration of each element was calculated from the spectral intensity. Table 3 shows the average value of the concentrations (mass%) of the three elements in which the observation place was changed. Phosphorus was detected from all the 0.85 M, 3 M, and 3.7 M phosphate-treated e-hydrate C12A7 compounds, and the phosphorus concentration on the surface of the powder was 0.65-8 mass%. In addition, the detected sodium originates in the phosphate used for the process.

As an example, the SEM photograph of the 3.7 M phosphate-treated electron C12A7 compound is shown in FIG. 2, and the energy dispersive X-ray (EDX) analysis spectrum is shown in FIG.

<pH change test over time>

(Time Change of pH of Ion Exchange Water Dispersing Surface Treated Powder)

0.0375 g and 7.5 mL of ion-exchanged water were each mixed with an untreated e-hydrate C12A7 compound, 0.85 M phosphate-treated e-hydrate C12A7 compound, 3 M phosphate-treated e-hydrate C12A7 compound, and 3.7 M phosphate-treated e-hydrate C12A7 compound, respectively, and 0.5 (w Each phosphate-treated evaporated C12A7 compound ion-exchange water dispersion was prepared at a concentration of / v)%. Each dispersion was stirred at a constant speed using a magnetic stirrer, and the change in pH over time was measured. The results are shown in FIG.

(Time Change of pH of Ion Exchange Water Dispersing 0.85 M Phosphate-treated Electron C12A7 Compound)

The 0.85 M phosphate-treated electronized C12A7 compound was dispersed in ion-exchanged water at concentrations of 0.1, 0.5, and 1.0 (w / v)%. Each dispersion was stirred at a constant speed using a magnetic stirrer, and the change in pH over time was measured. The results are shown in FIG.

At 0.5 (w / v)%, it was confirmed that the pH was maintained at pH 8 or lower for at least 120 minutes and at 1.0 (w / v)% for 360 minutes. These are observations in the state of being dispersed in a large amount of water. When used as a powder or non-aqueous skin external preparation or cosmetic, it may be in contact with moisture such as sweat, but since it is a small amount, the normal use time of cosmetics or the like can be sufficiently maintained at pH 8 or less. In addition, since sweat and the like dries and the contact time is short, the applied cosmetics can be kept neutral to acidic.

Water Dispersion Discoloration Test

(Time Change of Ion-exchange Water Dispersion of Surface-treated Powder)

0.0375 g of each of the untreated e-C12A7 compound, 0.85 M phosphate-treated EF C12A7 compound, 3 M phosphate-treated EF C12A7 compound, and saturated phosphate-treated EF C12A7 compound were mixed in 7.5 mL of ion-exchanged water, and 0.5 (w / Each phosphate-treated evaporated C12A7 compound ion exchange water dispersion was prepared at a v)% concentration. Each dispersion was stirred at a constant speed using a magnetic stirrer. The color of the dispersion liquid after 5 minutes and after 360 minutes immediately after dispersion is shown in Table 4.

As shown in Table 4, the untreated e-hydrate C12A7 compound was dispersed in ion-exchanged water, whitened after 5 minutes, and electrons were released. Dispersion of 0.85 M phosphate-treated electronized C12A7 compound in ion-exchanged water kept the green after 5 minutes and retained the electrons, but whitened after 360 minutes, and the electrons were released. In the case of 3M phosphate treatment and 3.7M phosphate treatment, it turned out that green is maintained more than 360 minutes. As a result, when it is used for powder and non-aqueous skin external preparations and cosmetics, since the amount of water to contact is small and it does not contact for a long time, it can fully use without discoloring.

Example 2

Oxidation Inhibitory Effect of Lipids (Evaluation of Antioxidant Activity by ESR)

As unsaturated lipids, squalene (Squalene, S3626 (Sigma-Aldrich), purity ≧ 98%) was used.

The spin trap reagent α-Phenyl-N-tert-butylnitrone (hereinafter referred to as PBN) was dissolved in tri (caprylic acid / capric acid) glyceryl to obtain a 400 mM solution.

(1) measuring sample preparation

To 0.35 mL of squalene, various unphosphorized or phosphate-treated evaporated C12A7 compounds obtained in Example 1 were mixed and irradiated with light of an ultra-high pressure mercury lamp (manufactured by Ushio Corporation) for 2 minutes under stirring. Next, 0.0875 mL of 400 mM PBN solution was mixed. The powder was removed by a filter to obtain an ESR measurement sample.

The density | concentrations of the unprocessed electronized C12A7 compound were made into three types of 10, 19, and 37 mass%. The concentration of the 0.85 M phosphate-treated electronized C12A7 compound was set to three types of 10, 19 and 37% by mass. The concentration of the 3M phosphate-treated electronized C12A7 compound was three types of 11, 19, and 37 mass%. The density | concentration of the 3.7 M phosphate treatment e-hydrate C12A7 compound was made into three types of 10, 19, and 37 mass%. The said concentration was shown by the mass concentration in the squalene dispersion liquid of each powder.

In addition, squalene prepared in the same manner without addition of the electronized C12A7 compound was used as a control.

(2) ESR measurement

For each sample, ESR spectra were measured. The device used EMX8 / 2.7 type (Burker). The radical scavenging ability was calculated | required by the following formula. The results are shown in Table 5. Table 5 is shown in the graph of FIG.

Signal strength of ESR spectrum of sample to which β = electron C12A7 compound was added

α = signal intensity of the reference ESR spectrum

The untreated e-hydrate C12A7 compound and the 0.85 M phosphate-treated e-hydrate C12A7 compound showed approximately the same antioxidant power.

The 3 M phosphate-treated e-hydrate C12A7 compound and the 3.7 M phosphate-treated e-hydrate C12A7 compound also showed antioxidant activity. Even if phosphate treatment is performed, the effect on antioxidant activity is small.

Example 3

Preparation of Electrolyzed C12A7 Compounds

An electronized C12A7 compound was prepared in the same manner as in Example 1, and ground to a smaller particle size. It was 2.1 * 10 <^18> cm <^{-3> when the} electron concentration was measured.

(Surface treatment)

A sodium dihydrogen phosphate aqueous solution of the concentration shown in Table 6 was prepared.

2.5 g of the electronized C12A7 compound and 50 mL of an aqueous solution of sodium dihydrogen phosphate were mixed and stirred with a stirrer for 10 minutes. The powder and the aqueous solution were separated by centrifugation, and the supernatant was discarded. After the powder was resuspended in ion-exchanged water, the supernatant was discarded by centrifugation to separate the powder and the aqueous solution. This operation was repeated 9 times to wash the aqueous solution adhering to the powder. The powder was vacuum dried to obtain a surface-treated powder. The electronized C12A7 compound surface-treated with the aqueous sodium dihydrogen phosphate solution of No. 4 is called a 5 M phosphate-treated electronized C12A7 compound.

(Measurement of Electron Concentration of Surface Treated Powder)

The spin concentration (= electron density) of the obtained phosphate-treated electronized C12A7 compound was measured by X-Band ESR. CuSO _4? E Concentration of the results, each of the samples calculated 5H ₂ O as a standard sample is to were as in Table 7. As shown in Table 7, even if phosphate treatment was performed, substantially no decrease in electron concentration occurred at the same level as the original electron concentration (2.1 × 10 ¹⁸ cm ⁻³ ).

(Infrared spectrum measurement of surface treated powder)

Infrared spectra were measured for each powder of an untreated electrolyzed C12A7 compound and a 5 M phosphate-treated electrolyzed C12A7 compound by using an infrared spectrometer Spectrum 400 during a Fourier transform manufactured by Perkin Elmer.

As shown in the infrared spectrum shown in FIG. 7, the infrared spectrum (see the curve shown in FIG. 7A) of the 5 M phosphate-treated electronized C12A7 compound showed absorption at 1095 cm ⁻¹ , but not in the untreated electronized C12A7 compound. Absorption of 1095 cm ⁻¹ was not observed (see the curve shown in FIG. 7B). This absorption is assumed to originate from the characteristic absorption of a phosphate group. The position of absorption estimated to originate from the characteristic absorption of this phosphate group is considered to fluctuate in the range of about 1100 +/- 50 cm <^-1> .

(Scanning Electron Microscopy and Energy Dispersive X-ray Analysis of Surface-treated Powders)

Surface-treated powders were observed using a scanning electron microscope (S-3400N manufactured by Hitachi High-Technologies), and the concentration of the surface-treated powders was measured using an energy dispersive X-ray analyzer (EMAX ENERGY EX-350 manufactured by HORIBA). Was measured.

The sample powder was compacted and fixed on the carbon tape. The part where the powder was fixed to the density which is detected in the carbon tape derived from the base carbon in the range of 10-20 mass% was made into the observation visual field, and elemental analysis by EDX was performed about the whole visual field. . Observation conditions were made into the low vacuum observation (30 Pa), magnification 3000 times, acceleration voltage 15 kV, probe current 60, process time 5, and live time 180 second.

As a result of the EDX analysis, the presence of carbon, oxygen, sodium, aluminum, phosphorus and calcium was confirmed. Except for the carbon derived from the carbon tape, the concentration of each element was calculated from the spectral intensity. The average value of the density | concentration (mass%) of each three elements which changed the observation place is shown in Table 8. Phosphoric acid was detected from the 5 M phosphate-treated e-hydrate C12A7 compound, and the phosphorus concentration on the powder surface was 6.4 mass%.

<pH change test over time>

(Time Change of pH of Ion Exchange Water Dispersing Surface Treated Powder)

0.0375 g of each of the untreated e-hydrate C12A7 compound and 5 M phosphate-treated e-hydrate C12A7 compound was mixed with 7.5 mL of ion-exchanged water, to prepare an ion-exchange water dispersion having a concentration of 0.5 (w / v)%. Each dispersion was stirred at a constant speed using a magnetic stirrer, and the change in pH over time was measured. The results are shown in Fig.

Water Dispersion Discoloration Test

(Time Change of Color of Ion Exchange Water Dispersion of Surface-treated Powder)

0.0375 g of each of the untreated e-hydrate C12A7 compound and 5 M phosphate-treated evaporated C12A7 compound was mixed with 7.5 mL of ion-exchanged water, and each phosphate-treated e-hydrate C12A7 compound ion-exchange water dispersion at a concentration of 0.5 (w / v)% was prepared. It prepared. Each dispersion was stirred at a constant speed using a magnetic stirrer. The color of the dispersion liquid after 5 minutes and 360 minutes after dispersion is shown in Table 9.

As shown in Table 9, the untreated e-carbide C12A7 compound was dispersed in ion-exchanged water and whitened after 5 minutes, and in the 5 M phosphate treatment, green was maintained for 360 minutes or more, while electrons were released. It became.

Example 4

Oxidation Inhibitory Effect of Lipids (Evaluation of Antioxidant Activity by ESR)

As unsaturated lipids, squalene (Squalene, S3626 (Sigma-Aldrich), purity ≧ 98%) was used.

The spin trap reagent α-Phenyl-N-tert-butylnitrone (hereinafter referred to as PBN) was dissolved in tri (caprylic acid / capric acid) glyceryl to obtain a 400 mM solution.

(1) measuring sample preparation

The untreated or phosphate-treated e-hydrate C12A7 compound having a small particle size prepared in Example 3 was mixed with 0.35 mL of squalene, and the light of an ultra-high pressure mercury lamp (manufactured by Ushio Corporation) was irradiated with stirring for 2 minutes. Next, 0.0875 mL of 400 mM PBN solution was mixed. The powder was removed by a filter to obtain an ESR measurement sample.

The concentration of the untreated electronized C12A7 compound was four types of 11, 19, 26, and 37 mass%. The concentration of the 5M phosphate-treated electronized C12A7 compound was three types of 5, 11 and 19 mass%. The said density | concentration was shown by the mass concentration as a squalene dispersion liquid of each powder.

In addition, squalene prepared in the same manner without addition of the electronized C12A7 compound was used as a control.

(2) ESR measurement

For each sample, ESR spectra were measured. The device used EMX8 / 2.7 type (Burker). The radical scavenging ability was calculated | required by the following formula. The results are shown in the graph of Table 10 and FIG.

Signal strength of ESR spectrum of sample to which β = electron C12A7 compound was added

α = signal intensity of the reference ESR spectrum

The untreated e-hydrate C12A7 compound and the 5 M phosphate-treated e-hydrate C12A7 compound showed antioxidant activity. It was confirmed that antioxidant activity is maintained even if phosphoric acid treatment is performed. In Example 2, as shown in Table 5, as the phosphate treatment concentration was increased, the radical scavenging ratio tended to decrease slightly. However, in the present Example 4, the radical scavenging rate increased slightly by 5 M phosphate treatment compared with the untreated one. The electronized C12A7 compound of Example 4 is pulverized so as to have a smaller particle size as compared with Example 2. According to the difference in particle size, there is a difference in the effect of the affinity between the surface treated with phosphate and squalene on the antioxidant power. Therefore, in Example 2 and Example 4, the relationship between the phosphate treatment and antioxidant power It is possible that a trend has occurred.

Example 5

Preparation of Powder Foundation

(mass%)

(1) Silicon-treated mica 20

(2) Siliconized Talc 22.4

(3) fluorinated titanium oxide 10

(4) Amino Acid Treatment Sericite 25

(5) siliconized iron sulfate 5

(6) Siliconized Bengala 2.5

(7) Silicon-treated black oxide 0.1

(8) 0.85 M phosphate treatment 1

  E-carbide C12A7 Compound

(9) Methylpolysiloxane (100cst) 11

(10) malic acid diisostearyl 3

(quite)

After stirring (1)-(8) with a Henschel mixer for 5 minutes, well-mixed (9)-(10) is gradually added, and it grind | pulverizes with a hammer mill. Then, it pressed to the intermediate dish.

Example 6

Eyeshadow Formulation

(mass%)

(1) Silicon treated mica 10

(2) Siliconized Talc 19

(3) Amino Acid Treatment Titanium Oxide 7

(4) amino acid treatment sericite 10

(5) nylon powder 10

(6) Silicon Powder 10

(7) fluorinated iron sulfate 5

(8) fluorinated bengalla 10

(9) Silicon treatment county office 3

(10) 0.85 M phosphate treatment 1

   E-carbide C12A7 Compound

(11) methylphenylpolysiloxane 8

(12) Cetyl 2-ethylhexanoate 7

(quite)

After stirring (1)-(10) with a Henschel mixer for 5 minutes, well-mixed (11)-(12) is gradually added, and it grind | pulverizes with a hammer mill. Then, it pressed to the intermediate dish.

Example 7

Preparation of sunburn prevention cream

(mass%)

(1) particulate titanium oxide 5

(2) Fine Particle Zinc Oxide 15

(3) cerium oxide 5

(4) 0.85 M phosphate treatment 1

  E-carbide C12A7 Compound

(5) octamethylcyclotetrasiloxane 20

(6) amino modified polyether silicone 1

(7) pivalic acid isostearyl 10

(8) behenyl alcohol 3

(9) Dipotassium glycyrrhinate 0.1

(10) Purified Water Residue

(quite)

The said (5)-(7) component is melt | dissolved by heating at 80 degreeC (phase A).

The components (1)-(4) are added and mixed in phase A (phase B).

After uniformly mixing (8) and (9), this is added to B phase and emulsified and mixed.

Example 8

Preparation of Liquid Foundation

(mass%)

(1) Olive Oil 2

(2) glyceryl trioctanoate 7

(3) trimethylsiloxy silicic acid 1

(4) silicic anhydride 6

(5) decamethylcyclopentanesiloxane 15

(6) octamethylcyclotetrasiloxane 15

(7) the amount of purified water

(8) 1,3-butylene glycol 4

(9) titanium oxide 12.5

10 mica 3

(11) 0.85 M phosphate treatment 1

   E-carbide C12A7 Compound

12.Fragrance 0.1

(13) Preservative 0.1

(quite)

The said components (1), (2), (12) and (13) were mixed and melted by heating (A phase).

The components (7) and (8) are mixed and dissolved (B phase).

The components (4), (9), (10) and (11) are pulverized after homogeneous mixing (C phase).

Components (3), (5) and (6) are mixed (D phase).

After mixing A phase and D phase, C phase is added and it mixes uniformly, and B phase is added and emulsified.

Example 9

Preparation of Plastic Pellets

(mass%)

(1) ABS resin 96

(2) calcium stearate 1

(3) 0.85 M phosphate treatment 3

  E-carbide C12A7 Compound

(quite)

The said (1)-(3) is extrusion-processed at 200 degreeC, and a pellet is produced.

Claims (11)

Electrons (e ⁻ ) of 2 × 10 ¹⁸ cm ⁻³ or more and less than 2.3 × 10 ²¹ cm ⁻³ , surface-treated using phosphate and detected by human energy from the surface of the powder by an energy dispersive X-ray analyzer including 12CaO? 7Al ₂ O ₃ compound. 1 × 10 ¹⁸ cm ⁻³ or more and 2.3 × 10 ²¹ cm ⁻³ electrons (e ⁻ ), surface treated using phosphate and detected by human energy from the powder surface by an energy dispersive X-ray analyzer. including 12CaO? 7Al ₂ O ₃ compound. The method of claim 1,
The surface with the phosphate treatment, 1 × 10 ¹⁸ ㎝ ^-3 or more, 2.3 × 10 ²¹ ㎝ ^-3 electron (e ^-) is less than? 12CaO containing 7Al ₂ O ₃ After suspending the compound in a phosphate aqueous solution, the compound It is a process which filters and isolate | separates powder, and is dried. The method according to claim 1 or 2,
The compound which shows pH of 8 or less of dispersion within 60 minutes immediately after disperse | distributing to ion-exchange water at the density | concentration of 0.5 mass%. 4. The method according to any one of claims 1 to 3,
Infrared spectrum absorption is confirmed at 1100 ± 50 cm ^-1 . Antioxidant which uses the compound as described in any one of Claims 1-5 as an active ingredient. A skin external preparation containing the antioxidant according to claim 6. The skin external preparation which does not contain water containing the antioxidant of Claim 6. The method according to claim 7 or 8,
A skin external preparation, wherein the skin external preparation is a makeup cosmetic. The antioxidant for plastic addition containing the compound as described in any one of Claims 1-4, or the antioxidant as described in Claim 6. Antioxidant for paint addition containing the compound as described in any one of Claims 1-5, or the antioxidant as described in Claim 6.

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