KR101410636B1 - Antioxidant - Google Patents

Abstract

The present invention relates to a method of producing a 12CaO · 7Al ₂ O ₃ compound and / or a 12SrO · 7Al ₂ O ₃ compound containing a hydrogen anion (H ^- ) having a concentration of 1 × 10 ¹⁸ cm ^-3 or more and their mixed crystals as an active ingredient ≪ / RTI >

Description

Antioxidant

The present invention relates to an antioxidant containing an inorganic powder containing hydrogen anion.

The composition of the inorganic compound (12CaO · 7Al ₂ O ₃ compound, 12SrO · 7Al ₂ O ₃ compound, or 12 ((1-x) CaO · xSrO) · 7Al 2 O 3 (0 <x <1) containing hydrogen anion · 7Al ₂ O ₃ with a 12CaO · 7Al ₂ O ₃ mixed crystal 12SrO (混晶) compounds) represented by the following has been known (Patent Document 1: WO2003 / 089373 JP). These compounds are known to be able to develop in a room-temperature atmosphere the ability to permanently switch from an insulator to an electrical conductor by light irradiation. However, it has not been known that these compounds have an excellent antioxidative effect.

Antioxidant activity in living organisms is important for maintaining health. Common antioxidants (radical scavengers) give electrons to radicals and stably form hole-electrons. In this case, the antioxidants themselves become radicals, which are generally stable and are converted into nonradical species by various pathways. Compounds having a phenol skeleton or thiol group generally have antioxidant activity. Antioxidants are used as antioxidants for foods and fats, and also as medicines. Natural antioxidants include tocopherol (vitamin E), sesaminol (present in sesame oil), resveratrol (present in red wine) and catechin (present in tea).

In addition, antioxidants have been used as antioxidants. It is used as an additive for paints, oils, foods, plastics and the like.

Patent Document 1: WO2003 / 089373

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-26608

Patent Document 3: Japanese Patent No. 3533648

DISCLOSURE OF INVENTION

Problems to be solved by the invention

And to provide a novel antioxidant.

Means for solving the problem

An antioxidant comprising a powder of an inorganic compound containing a hydrogen anion (a 12CaO · 7Al ₂ O ₃ compound, a 12SrO · 7Al ₂ O ₃ compound, or a mixture of 12CaO · 7Al ₂ O ₃ and 12SrO · 7Al ₂ O ₃ ) And applications thereof.

The main structure of the invention of the present application is as follows.

(1) An antioxidant comprising 12CaO · 7Al ₂ O ₃ compounds and / or 12SrO · 7Al ₂ O ₃ compounds containing hydrogen anions (H ^- ) having a concentration of 1 × 10 ¹⁸ cm ^-3 or more and their mixed crystals as active ingredients.

(2) An external preparation for skin containing an antioxidant according to (1).

(3) A cosmetic comprising the antioxidant according to (1).

(4) A whitening agent containing an antioxidant according to (1).

(5) An antioxidant for plastic addition containing an antioxidant according to (1).

(6) An antioxidant for paint addition comprising an antioxidant according to (1).

Effects of the Invention

A novel antioxidant can be provided.

The inorganic compound powder containing the hydrogen anion of the present invention exerts an excellent function as an antioxidant. Plastics, paints, cosmetics, preservatives, and the like.

Brief Description of Drawings

Fig. 1 is a graph showing the results of quantifying the amount of hydrogen anion by IR and SIMS.

2 is a graph showing the results of ESR spectra of a sample solution of a pure solvent.

3 is a graph showing the radical scavenging ability of the samples A-2 to A-4 of Example 3. Fig.

4 is a graph showing the radical scavenging ability of the samples B-2 to B-4 of Example 3. Fig.

5 is a graph showing the radical scavenging ability of the samples C-2 to C-4 using the solvent C of Example 4. Fig.

6 is a graph showing the radical scavenging ability of the samples D-2 to D-4 using the solvent D of Example 4.

7 is a chart showing the scavenging ability of a titanium dioxide light-induced hydroxy radical by the ESR method using the sample 10 of Example 10. Fig.

Carrying out the invention  Best form for

It is according to the invention as a starting material, pure 12CaO · 7Al ₂ O ₃ compound (hereinafter, when described as C12A7 also) as long as the even and, that the nitro-form crystal structure in my of C12A7 unique in the process is not destroyed, calcium And a mixed crystal or a solid solution (hereinafter abbreviated as equivalent) having a crystal structure equivalent to a C 12 A 7 compound in which a part or the whole of aluminum is substituted with another element.

A material having a crystal structure equivalent to the C12A7 compound is present 12SrO · 7A1 ₂ O ₃ is known, and it is possible to change freely the mixing ratio of Ca and Sr. That is, it may be a mixed crystal compound of 12CaO · 7Al ₂ O ₃ and 12SrO · 7A1 ₂ O ₃ . In addition, the kind or amount of the anion initially enclosed does not greatly affect the introduction effect of the hydrogen anion. In addition, the form may be any of powder, film, polycrystal, and single crystal.

The starting material, C12A7, is synthesized by solid phase reaction at a calcination temperature of 1200 ° C or more and less than 1415 ° C using a raw material containing calcium (Ca) and aluminum (Al) in an atomic equivalent ratio of 12:14. A representative raw material is a mixture of calcium carbonate and aluminum oxide.

The single crystal can be obtained by the floating-bed melting method (FZ method) using the C12A7 sintered body obtained in the solid-phase reaction as a precursor. To grow the C12A7 single crystal, the precursor rod is lifted while condensing infrared rays on the rod-shaped ceramic precursor, thereby moving the melting zone and continuously growing the single crystal at the interface of the melt-solidified portion. The present inventors have disclosed a method for producing a C12A7 compound single crystal containing a high concentration of active oxygen species and a C12A7 single crystal without bubbles in Patent Document 3 (Japanese Patent No. 3533648).

C12A7 and the equivalent material of the starting material are heated in an atmosphere containing not less than 1000 ppm of hydrogen, preferably not more than oxygen and moisture, in an atmosphere containing not less than 20 vol% of hydrogen at 800 DEG C or higher, preferably 1000 DEG C or higher , At a temperature of less than 1350 ° C, more preferably at a temperature of about 1300 ° C, depending on the form of the starting material, and then cooled. In order to obtain an atmosphere containing hydrogen, hydrogen may be charged into a container made of a material capable of withstanding a high-temperature heat treatment such as quartz glass or tantalum, and the starting material may be sealed therein. At this time, instead of filling the hydrogen gas, a substance capable of generating hydrogen by a chemical reaction may be enclosed together. In the case of pure C12A7, it is dissolved in an atmosphere containing hydrogen at a temperature higher than 1350 DEG C, and the crystal structure is lost.

When the concentration of hydrogen in the atmosphere subjected to the heat treatment is 1000 ppm or less, the amount of hydrogen anion introduced into C12A7 and the equivalent substance is not more than 1 x 10 ¹⁸ cm ^-3 , so that excellent antioxidative action is hardly obtained. In addition, the more the low-temperature heat treatment temperature is equal C12A7 and hydrogen ions incorporated into the material a hydroxyl ion (OH ^-) are liable to be substituted with less than 800 ℃ When the amount of the hydrogen-anion 1 × 10 ¹⁸ ㎝ ^-3 since the under , It is difficult to obtain an excellent antioxidant function.

The cooling rate may be normal natural cooling of an electric furnace, but it is preferably quenched. When the heat treatment temperature is low, the amount of hydrogen anion is made to be not less than 1 x 10 ¹⁸ cm ^-3 by quenching.

The material after the above high-temperature treatment is colorless transparent when pure C12A7 is a raw material, and white when it is powder. When the reduction condition by the hydrogen gas is strong, electrons are introduced into a part of the cage to show light green. In this case, by keeping the temperature between 300 DEG C and 450 DEG C for about 10 minutes, electrons can be lost without reducing the amount of the hydrogen anion, thereby making the state transparent or white.

The state that the hydrogen anion is included or introduced indicates that the hydrogen anion is trapped in the space of the cage of the C12A7 crystal. It is known that the unit lattice of the C 12 A 7 crystal has a lattice constant of about 1.2 nm and is represented by a composition of [Ca ₂₄ Al ₂₈ O ₆₄ ] ⁴⁺ . When all positive charges of +4 per unit lattice are compensated for by the introduction of hydrogen anions, the number of hydrogen anions contained in C12A7 crystals is expected to be 2.3 × 10 ²¹ per cubic centimeter maximum.

The inorganic powder containing a hydrogen anion exerts an excellent function as an antioxidant. Plastics, paints or cosmetics, medicines, fats, and the like.

Example 1

The C12A7 single crystal produced by the floating-bed melting (FZ) method was processed into a mirror-polished plate with a thickness of 300 mu m. This was heat-treated in oxygen at 1350 DEG C for 6 hours (Sample A). Subsequently, the mixture was maintained at 1300 占 폚 for 2 hours in a mixed gas stream of 20% volume hydrogen-80% volume nitrogen, and then quickly cooled in the same atmosphere to introduce hydrogen anion into the C12A7 crystal (Sample B).

Subsequently, the temperature was raised to 800 ° C in the air, and then the hydrogen anion was removed or cooled to a hydroxyl group (OH ^- ) (sample C). The concentration of hydroxyl groups in each sample was determined by the infrared absorption intensity at 3560 cm ^-1 . In addition, the concentration of the total amount of hydrogen contained in each sample was quantified by secondary ion mass spectrometry (SIMS).

In the samples A and C, hydrogen almost entirely forms a hydroxyl group as a proton. In sample B, hydrogen exists as hydrogen anion in addition to proton. A calibration curve of the proton concentration can be prepared from the infrared absorption of the samples A and C and the quantitative value of the SIMS and the concentration of the hydrogen anion in the sample B can be inferred therefrom. This calculation method is shown in Fig. The hydrogen concentration in the sample B as the hydrogen anion was estimated to be 2 x 10 ²⁰ cm ^-3 .

Referring to FIG. 5, a hydrogen anion was introduced into a C12A7 sintered body having a density of about 80% by performing heat treatment under the same conditions as in the case of the sample B. Since the condition is the same as that of the sample B, the concentration of the hydrogen anion was estimated to be 2 × 10 ²⁰ cm ^-3 . This sintered body was made into a powder by performing a planetary ball mill in which ethanol was used as a dispersion medium and alumina balls were pulverized. The specific surface area of the powder was estimated to be about 2 m &lt; 2 &gt; / g by the BET method.

Example 2

DPPH radical Scatters  Measure

(1) Preparation of DPPH solution

DPPH (1,1'-diphenyl-2-picrylhydrazyl, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 100% ethanol to prepare 0.00394 w / v% solution.

(2) Preparation of sample solution

A 0.1 w / v% dispersion of the sample B prepared in Example 1 was prepared using pure water as a solvent. Ultrasonic waves were applied for 5 minutes to pulverize the agglomerates, followed by stirring for about 1 hour with a stirrer. Since the powder easily precipitates in pure water, it was stirred with a stirrer just before mixing with the DPPH solution. Pure water was used as a control for the sample solution of the pure solvent.

(3) Measurement of ESR spectrum

(Device ESR-JES-TE200: JEOL)

(Measurement of DPPH radical and lipid peroxidation ability), and the measurement of the DPPH radical and the lipid peroxidation activity were carried out in the same manner as in Example 1, , Response time: 0.03 sec.

100 μl of the DPPH solution and 100 μl of the sample solution of the pure solvent (1/2 dilution, 1/4 dilution, and 1/10 dilution each based on 0.1 w / v%) were mixed in a plate reader plate for approximately 2 minutes After reacting with the radical, the ESR spectrum was measured. The measurement results are shown in Fig.

Sample solution of pure solvent

In the control (pure water), a spectrum specific to the presence of radicals was observed. When the 0.1 w / v% sample B dispersion was mixed, the peak disappeared and the radicals were observed to be erased. To a solution of 0.1 w / v% powder dispersion diluted to 0.01 w / v% (1/10 dilution), 0.025 w / v% (1/4 dilution) and 0.05 w / v% (1/2 dilution) Were measured in the same manner, the dependency of the powder concentration on the radical scavenging ability was confirmed. The radical scavenging ability was obtained by the following equation.

(Formula 1) Radical scavenging ability (%) = (1 -? /?) 100

Where β = peak height of ESR spectrum of sample B dispersion + DPPH solution

α = peak (pure) + peak height of ESR spectrum of DPPH solution

(4) Results

The radical scavenging ability of the sample B dispersion at concentrations of 0.05 w / v%, 0.025 w / v% and 0.01 w / v% was 83%, 43% and 8%. It was suggested that the radical scavenging ability has a linear concentration dependency. It was also confirmed that the IC50 was 0.021 w / v%. From this result, it was confirmed that the antioxidative ability (DPPH radical scavenging ability) of the sample B was confirmed.

Example 3

On the lipid oxidation inhibitory effect (squalene, oleic acid ESR On by Antioxidant ability  evaluation)

(1) Solvent

Squalane (Kishimoto special liver oil purity: 99.5% antioxidant free) and oleic acid (Wako Pure Chemical Industries Grade 1) were used.

(2) Spin trap reagent preparation

The spin trap reagent α-Phenyl-N-tert-B-butylnitrone (hereinafter referred to as αPBN) was dissolved in tri (caprylic / capric acid) glyceryl (using ultrasonic waves) to prepare a 400 mM solution.

(3) Preparation of measurement sample

The sample B of Example 1 and the spin trap reagent (? PBN) solution were added to the solvent sample, and the mixture was adjusted to the compounding amount shown in Table 1 to obtain an ESR measurement sample. The concentration of the sample B was determined as the weight percentage determined by (sample B weight) / (solvent weight) x 100.

(4) ESR measurement

Each sample was irradiated with UV-A wave, and the amount of radical generation when the emulsion was oxidized was measured by ESR. Table 1 shows the UV irradiation time.

The radical scavenging ability was determined by the following formula. Fig. 3 shows A-2 to A-4, and Fig. 4 shows B-2 to B-4.

(Formula 2) Radical scavenging activity (%) = (1 -? /?) × 100

? = Peak height of ESR spectrum of sample B dispersion (A-2 to A-4 or B-2 to B-4)

α = Peak height of ESR spectrum of control (A-1 when β is A-2 to A-4) or B-1 (when β is B-2 to B-4)

(5) Results

The radical scavenging activity was 55%, 35% and 15% as a result of adding 5 w / w%, 2.5 w / w% and 1.25 w / w% of powder to the squalene (sample B of Example 1). Showed significant antioxidative effects depending on the concentration of the powder. It was also confirmed that the IC50 was 4.2 w / w%. The addition of 5 w / w%, 2.5 w / w%, and 1.25 w / w% of powder (sample B of Example 1) to oleic acid resulted in radical scavenging ability of 50%, 41% and 33%. Showed significant antioxidative effects depending on the concentration of the powder. It was also confirmed that the IC50 was 4.9 w / w%.

Example 4

On lipid oxidation inhibition effect (due to ESR of saturated fatty acid + unsaturated fatty acid (oleic acid, squalene) Antioxidant ability  evaluation)

· Oleic acid + tri (caprylic / capric acid) glyceryl

· Squalene + tree (caprylic / capric acid) glyceryl

(1) Solvent preparation

Sample preparation of ESR measurement was carried out. The following three emulsions were mixed and used. The prepared solvent is as follows.

Solvent C a: c = 5: 5 (weight ratio) solvent D b: c = 5: 5 (weight ratio)

a squalane (99% of Wako Pure Chemical Industries Limited α-tocopherol 0.05% antioxidant)

b oleic acid (Wako Pure Chemical Industries Class 1)

c tree (caprylic / capric acid) glyceryl (Myrtol 318, Cognis)

(2) Measurement sample preparation

With respect to the solvents C and D, samples B and? PBN of Example 1 were added to the blend amounts shown in Table 2 to prepare ESR measurement samples (C-1 to C-4, D-1 to D-4). The concentration of the sample B was determined as the weight percentage determined by (sample B weight) / (solvent weight) x 100.

(3) ESR measurement

Each sample was irradiated with UV-A wave, and the amount of radical generation when the emulsion was oxidized was measured by ESR. The UV irradiation time is shown in Table 2 above.

The radical scavenging ability was determined by the following formula. Samples C-2 to C-4 using solvent C are shown in Fig. 5, and samples D-2 to D-4 using solvent D are shown in Fig.

(Formula 3) Radical scavenging activity (%) = (1 -? /?) 100

? = Peak height of the ESR spectrum of the sample B dispersion (C-2 to C-4 or D-2 to D-4)

α = Peak height of ESR spectrum of control (C-1 when β is C-2 to C-4) or D-1 (when β is D-2 to D-4)

(4) Results

The results obtained by adding 2.0 w / w%, 1.0 w / w% and 0.5 w / w% of the sample B of Example 1 to the solvent C (squalene: tri (caprylic / capric acid) glyceryl = 5: , The radical scavenging ability was 40%, 27%, and 9%. Showed significant antioxidative effects depending on the concentration of the powder. It was also confirmed that the IC50 was 2.9 w / w%. 2.0 w / w%, 1.0 w / w%, and 0.5 w / w% of powder (sample B of Example 1) were added to the solvent D (oleic acid: tri (caprylic acid / capric acid) glyceryl = 5: As a result, the radical scavenging ability was 66%, 42%, and 26%. Showed significant antioxidative effects depending on the concentration of the powder. It was also confirmed that the IC50 was 1.2 w / w%.

Squalene and oleic acid were each diluted to 50% with TG (tri (caprylic / capric acid) glyceryl), the radicals due to the oxidation of squalene and oleic acid were removed by the powder of the sample B in the same manner as in Example 3, Dependent.

Example 5

Preparation of plastic pellets

(Production method) The above (1) to (3) are extruded at 200 占 폚 to produce pellets.

Example 6

Preparation of liquid foundation

(quite)

The components (1), (2), (12) and (13) were mixed and heated to dissolve (phase A). Components (7) and (8) are mixed and dissolved (phase B). The components (4), (9), (10) and (11) are homogeneously mixed and pulverized (phase C). Components (3), (5) and (6) are mixed (D phase). After the A phase and the D phase are mixed, the C phase is added and homogeneously mixed, and the B phase is added and emulsified.

Example 7

Preparation of sunscreen cream

(Preparation method) The above components (5) to (7) are dissolved by heating at 80 占 폚 (phase A). Components (1) to (4) are added to phase A and mixed (phase B). (8) and (9) are homogeneously mixed, and this is added to the phase B and emulsified and mixed.

Example 8

Preparation of powder foundation

(Preparation method) (1) to (8) are stirred with a Henschel mixer for 5 minutes, then the well mixed (9) to (10) are gradually added and crushed with a hammer mill. Thereafter, it was pressed in a middle plate.

Example 9

Preparation of eye shadow

(Preparation method) (1) to (10) are stirred with a Henschel mixer for 5 minutes, and then the well mixed (11) to (12) are gradually added and pulverized with a hammer mill. Thereafter, it was pressed in a middle plate.

Example 10

ESR Titanium dioxide Light irradiation  Derived hydroxy Radical Scatters  evaluation

When anatase titanium dioxide is irradiated with light having a wavelength of 380 nm or less, radicals are generated by a photocatalytic reaction. Whether or not the radicals generated by irradiating light onto the titanium dioxide fine particle water dispersion was erased from the sample B prepared in Example 1 was evaluated by electron spin resonance (ESR). And the life of the radical was extended by coexistence of spin trap reagent DMPO (5,5-dimethyl-1-pyrroline-N-oxide).

(Test Methods)

Anatase-type titanium dioxide fine particles (average particle size 180 nm) 20 μL of a 0.5% (w / v) dispersion, 180 μL of a sample solution and 200 μL of a 10 mM DMPO aqueous solution were mixed (400 μL in total) For 1 minute. The mixed dispersion irradiated with ultraviolet rays was enclosed in the solution cell for ESR, and the ESR spectrum of DMPO-OH was measured.

As the sample solution, ion-exchanged water (control) and sample B dispersion were used. The sample B dispersion was used for the measurement immediately after the sample B was dispersed in water. The concentration of the sample B in the mixed dispersion was adjusted to be 0.5% or less and the concentration of the sample B dispersion was adjusted to 1.22% (w / v), 1.67% (w / v), 2.22% (w / v) (w / v), 0.75% (w / v), 1.0% (w / v) and 4.5% (w / v).

The device EMX8 / 2.7 (Burker Biospin) was used for ESR measurement. The measurement conditions were determined using Auto tune.

The radical scavenging ability was obtained by the following equation.

(Formula 3) Radical scavenging rate (%) = (1 -? /?) 100

β = the second peak height from the author's side of the ESR spectrum of the mixed dispersion after irradiation with ultraviolet light when the sample B dispersion is used as the sample solution.

α = the second peak height from the author's side of the ESR spectrum of the mixed dispersion after irradiation with ultraviolet rays when ion-exchanged water (control) was used as the sample solution.

(result)

The radical scavenging ability was not observed at 0.5% (w / v) and 0.75% (w / v) of the sample B in the mixed dispersion but the radical scavenging ability was 38% and 4.5% (w / v) showed a scavenging ability of 86%. The results are shown in Fig.

The inorganic powder containing the hydrogen anion of the present invention exerts an excellent function as an antioxidant.

Plastic, paints or cosmetics, and the like, it can be used in an arbitrary amount as an antioxidant.

Claims (6)

1 × 10 ¹⁸ ㎝ ^-3 or more hydrogen anion concentration (H ^-) of, 12CaO · 7Al ₂ O ₃ compound, 12SrO · 7Al ₂ O ₃ containing compound, and one is selected from the mixed crystal (混晶) compound of the compound Or more as an active ingredient. An external preparation for skin containing the antioxidant of claim 1. A cosmetic comprising the antioxidant of claim 1. A whitening agent containing the antioxidant of claim 1. An antioxidant for plastic addition containing the antioxidant of claim 1. An antioxidant for paint addition comprising the antioxidant of claim 1.

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