JP6868520B2 - Adsorbent used to adsorb functional components - Google Patents

Description

The present invention relates to an adsorbent used for adsorbing a functional component contained in various animals and plants, added to supplements, beverages, etc., or used as a pharmaceutical product.

In recent years, health consciousness has extracted components having medical effects contained in various animals and plants, added them to supplements, beverages, etc., or used them as pharmaceuticals, etc., and the components having such medical effects have functions. It is called a sex component.

Typical examples of the above-mentioned functional components are lecithin, astaxanthin, quercetin glycoside, chlorogenic acid and isoflavone, and further, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and tea catechin. And gamma oryzanol are also known.

Lecithin is represented by the following formula, for example, contains phospholipids contained in egg yolk, soybeans, etc., has a penetrating action of penetrating the skin and mucous membranes, and is used as a therapeutic agent for hemorrhoids and skin diseases. It is also used as a material for pharmaceutical liposomes, a fat emulsion for intravenous injection, and the like.

Astaxanthin is represented by the following formula and is a pigment substance contained in algae, shrimp, sea bream, salmon and the like. It has a high antioxidant activity and is thought to have a function of protecting the living body from ultraviolet rays and lipid peroxidation reactions, and is used in supplements, health foods, skin care products, and the like.

Quercetin glycosides (for example, rutin) are represented by the following formulas and are contained in buckwheat noodles and citrus fruits. Antioxidant effect, anti-inflammatory effect, anti-arteriosclerosis effect, prevention of cerebrovascular disease, antitumor effect, antihypertensive effect, vascular relaxation effect, etc. have been reported and are used as pharmaceuticals.

Chlorogenic acid is represented by the following formula and is contained in coffee beans and the like. It is considered that water and the like are imparted with miscellaneous tastes such as astringency, acidity and sweetness, and are added to various beverages and the like.

Isoflavones are contained in soybeans and the like and are represented by the following formula. As a compound, it is generally marketed as genistein or the like. It is said to be effective in improving menopause and preventing osteoporosis, and is used as a supplement.

Linolenic acid (α-linolenic acid), that is, all-cis-9,12,15-octadecatorienic acid is abundantly contained in vegetable oils and is represented by the following formula. It is an essential fatty acid that is an essential nutrient to be ingested, and is used in supplements or in foods such as beverages and jellies.

Eicosapentaenoic acid (EPA) is a long-chain unsaturated fatty acid having 20 carbon atoms obtained from fish oil foods, cod liver oil, herring, mackerel, sardines, Antarctic krill and the like, and is represented by the following formula. It has an inhibitory effect on platelet aggregation and is used as a therapeutic agent for hyperlipidemia and arteriosclerosis.

Docosahexaenoic acid (DHA) is an unsaturated fatty acid having 22 carbon atoms, which is abundantly contained in fish oils such as mackerel and sardines, and is represented by the following formula. It is a major component of fatty acids contained in phospholipids of semen, brain, and retina, and exhibits many physiological actions such as learning function improving action, anticancer action, blood lipid lowering action, retinal reflex improving action, and blood pressure lowering action. , A substance being studied as a drug.

この化合物の光学異性体（エピカテキン）や、その誘導体、具体的には、ヒドロキシ体（エピガロカテキン）、これらの没食子酸エステル（エピカテキンガレート、エピガロカテキンガレート）は、茶カテキンとして知られる緑茶の渋み成分であり、茶葉から抽出される。このような茶カテキンは、血圧上昇抑制作用、血中コレステロール調節作用、血糖値調節作用などの種々の生理活性を有しており、例えば飲料等に配合して健康食品として、或いはサプリメントとして販売されている。また、抗菌性を有していることも知られており、樹脂に配合して抗菌性部材としての使用も提案されている。
尚、抗菌性部材として使用する場合には、変色や着色を抑え、さらには水による抽出を防止するために、シリカ等の無機材料に担持されて使用される。 Catechin is a compound of _{C 15} H ₁₄ O ₆ represented by the following formula.

The optical isomer (epicatechin) of this compound, its derivatives, specifically, the hydroxy form (epigallocatechin), and their gallic acid esters (epicatechin gallate, epigallocatechin gallate) are known as tea catechin. It is an astringent ingredient of green tea and is extracted from tea leaves. Such tea catechin has various physiological activities such as an effect of suppressing an increase in blood pressure, an effect of regulating blood cholesterol, and an effect of regulating blood sugar level. For example, it is blended in a beverage or the like and sold as a health food or as a supplement. ing. It is also known to have antibacterial properties, and it has been proposed to use it as an antibacterial member by blending it with a resin.
When used as an antibacterial member, it is supported on an inorganic material such as silica in order to suppress discoloration and coloring and to prevent extraction by water.

Gamma-oryzanol is contained in the lipid of rice bran, is a general term for esters of ferulic acid and sterols, and is a substance having CAS Registry Number [11042-64-1]. It has the effect of suppressing the absorption of cholesterol and the effect on menopausal disorders, and is used as a medicine. It is also added to cosmetics to prevent UV rays.

All of the above functional components are isolated and used for use by extraction from animals and plants containing them (see, for example, Patent Documents 1 to 7), but are used for isolation from the extract. As the adsorbent, acidic clay, activated clay, silica gel, alumina, activated carbon and the like are used, and no detailed study has been conducted on the adsorbent.

Japanese Unexamined Patent Publication No. 2015-142560 Japanese Unexamined Patent Publication No. 05-068585 Japanese Unexamined Patent Publication No. 54-101412 Japanese Unexamined Patent Publication No. 2007-54056 Japanese Unexamined Patent Publication No. 08-283283 Japanese Unexamined Patent Publication No. 2005-82902 Tokukousho 32-6395 Gazette

As a result of examining the adsorbent of the above-mentioned functional component, the present inventors have obtained silica-magnesia composite particles in which silica particles and magnesia particles are integrally composited from the aqueous solution or alcohol solution of the above-mentioned functional components. We obtained the finding that it can effectively adsorb sex components.

Therefore, an object of the present invention is to provide an adsorbent for functional components collected from animals and plants.

According to the present invention, it is selected from the group consisting of lecithin, astaxanthin, quercetin glycoside, chlorogenic acid, isoflavone, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), catechin and its derivatives, and gamma oryzanol. It is an adsorbent used for adsorbing functional components, and is composed of silica-magnesia composite particles in which silica particles and magnesia particles are integrally composited, and has an anion adsorption capacity of 18 to 74 mmol / 100 g represented by the amount of Orange II adsorbed. An adsorbent characterized by being in the range of

In the adsorbent of the present invention, the silica component and the magnesia component are expressed by the following formula (1):
R = Sm / Mm (1)
In the formula, Sm is the content (mass%) of the silica component in terms of _{SiO 2.}
Mm is the content (mass%) of the magnesia component in terms of MgO.
It is preferable that the mass ratio (R) represented by is contained in a ratio of 0.1 ≦ R ≦ 3.5.

The adsorbent of the present invention can effectively adsorb the functional components contained in these solutions by adding the adsorbent to the aqueous solution or alcohol solution containing the various functional components described above. Therefore, these functional components can be isolated by putting them into a solution extracted from various animals and plants.

Further, in the present invention, the silica-magnesia composite particles used as an adsorbent are composites of silica particles and magnesia particles, and are not magnesium silicate which is not approved for use as a food additive. Therefore, the functional ingredient isolated using the adsorbent of the present invention can be used in supplements, beverages, and pharmaceuticals without any particular limitation.
Furthermore, the silica-magnesia composite particles do not have metal ions such as Al ions, Ca ions, and Fe ions that cause the flavor of the beverage to be impaired. Therefore, these metal ions are not mixed in the functional components desorbed from this adsorbent, and even when the isolated functional components are added to a beverage or the like, the flavor of the beverage can be maintained. There is no inconvenience of damaging it.

<Adsorbent>
The adsorbent of the present invention used for adsorbing functional components consists of silica-magnesia composite particles.
That is, the silica-magnesia composite particles have a structure in which the silica particles and the magnesia particles are in close contact with each other at a very fine level (for example, nano level) and are integrated without being separated. It does not mean that magnesium silicate is produced by reacting with magnesia, or that atoms are recombined by the reaction. This can be confirmed by, for example, XRD measurement not expressing a peak peculiar to magnesium silicate and the amount of adsorption to the anionic dye (Orange II).

For example, in the silica-magnesia composite particles used as an adsorbent, the amount of Orange II adsorbed measured by the method shown in Examples described later is in the range of 18 to 74 mmol / 100 g. Such an orange II adsorption amount is derived from the anion adsorption property peculiar to magnesia, and silica does not exhibit such an anion adsorption property. Therefore, the orange II adsorption amount is in the above range. , This composite particle means that the silica particle and the magnesia particle are composited without reacting. That is, when magnesium silicate is produced by the reaction of silica and magnesia, the adsorptivity of magnesia is impaired, so that the amount of Orange II adsorbed is considerably smaller than the above range. Further, when the silica particles and the magnesia particles are not compositely integrated and exist as a mere mixture, the amount of Orange II adsorbed shows a value higher than the above range or varies greatly. This is because the silica particles that do not exhibit anion adsorption and the magnesia particles that exhibit anion adsorption exist independently.

As described above, the composite particles in which the silica particles and the magnesia particles are compositely integrated show excellent adsorptivity to various functional components as shown in Examples described later, and only the silica particles or the magnesia particles are exhibited. Then, the adsorptivity to the functional component is considerably low, and even a simple mixture of silica particles and magnesia particles has low adsorptivity to the functional component. The adsorptivity of such composite particles to functional components has been confirmed as a phenomenon by many experiments, and the reason why the excellent adsorptivity is generated has not been theoretically elucidated. However, in the present inventors, the physical adsorption exhibited by the silica particles and the chemical adsorption property exhibited by the magnesia particles act synergistically with respect to the functional component by the composite integration of the silica particles and the magnesia particles. It is presumed that excellent adsorptivity is exhibited.

Further, in the adsorbent of the present invention, the silica component and the magnesia component are represented by the following formula (1):
R = Sm / Mm (1)
In the formula, Sm is the content (mass%) of the silica component in terms of _{SiO 2.}
Mm is the content (mass%) of the magnesia component in terms of MgO.
It is preferable that the mass ratio (R) represented by is contained in a ratio of 0.1 ≦ R ≦ 3.5.
That is, since silica and magnesia are present in the above-mentioned quantitative ratio, the composite integrated state is stably maintained. For example, when the mass ratio (R) is more than 3.5 or less than 0.1, silica or magnesia is likely to fall off, which makes the adsorptivity to the functional component unstable and causes variation. This is because it becomes easier.

Further, in such silica-magnesia composite particles, since the silica component and the magnesia component are not liberated from each other and are closely compounded, the pH (25 ° C.) of the suspension having a concentration of 5% by mass thereof is usually high. It is in the range of 6.0 to 10.0.

In the present invention, the silica-magnesia composite particle used as an adsorbent is obtained by homogeneously mixing silica (A) and magnesia or its hydrate (B) in the presence of water to form an aqueous slurry (homogeneous mixing). ), Then it can be produced by aging and further removing water.
The amount ratio of silica (A) to magnesia or its hydrate (B) is set so that the mass ratio (R) represented by the above formula (1) is 0.1 to 3.5. do it.

As the raw material silica (A), an amorphous water-containing type is preferable, and it may be produced by either a gel method or a sedimentation method, but one having small primary particles is preferable. A BET specific surface area of 40 m ² / g or more, particularly 140 m ² / g or more is preferable.
Further, as the magnesia or its hydrate (B), those having small crystals and not being carbonated with time are preferable. For example, magnesia powder having a BET specific surface area of 2 m ² / g or more, preferably 20 m ² / g or more, particularly preferably 50 m ² / g or more is used.

In the presence of water between the above silica (A) and magnesia or its hydrate (B), for example, in homogeneous mixing in water, silica (silicon dioxide), which is one of the raw materials, is colloidal particles or finely aggregated particles ( Primary to secondary particles) can be solved. The other magnesia (magnesium oxide) also hardly dissolves when it is put into water and stirred or crushed, but its crystals (or newly formed hydrate) are formed by partial hydration of the surface of magnesia particles. Part or all of the crystals) are disintegrated or exfoliated to form fine particles composed of magnesia (magnesium oxide) and / or magnesium oxide hydrate and dispersed in water.

In the preparation of the aqueous slurry in the presence of water as described above, there are no restrictions on the order of adding the raw materials (A) and (B) and water, but when aggregation or gelation phenomenon (thickening) occurs, the above-mentioned There is a risk that the progress of fine particle formation (nanoparticle formation) and integral complexation will be hindered. Therefore, it is preferable that the solid content concentration of the aqueous slurry is low. On the other hand, from the viewpoint of productivity and economy, the higher the solid content concentration is, the better. Therefore, the solid content concentration is preferably 3 to 15% by mass, particularly preferably 8 to 13% by mass.

In the aging step, water is removed from the slurry in which these fine particles are uniformly dispersed, and as the solid content concentration increases, the silica particles (A) and the magnesia particles (B) gradually or rapidly change. The silica-magnesia composite particles of interest can be obtained by approaching each other and reaching an integrally composited form (completion of integrally composited) without involving chemical bonds that involve atom exchange or recombination.

The above-mentioned homogeneous mixing and aging are preferably carried out at 100 ° C. or lower, preferably at 50 to 97 ° C., and at 50 to 79 ° C., gelation is effectively prevented and composite integration is carried out in a short time. It is suitable for doing.

Homogeneous mixing and aging are generally carried out under stirring in a stirring tank equipped with a stirring blade, but can also be carried out under pulverization or dispersion by a wet ball mill or a colloid mill. It is necessary to carry out homogeneous mixing and aging for at least 0.5 hours, although it depends on the charging capacity and the like. Further, the higher the temperature, the higher the fluidity of the nanoparticles and the more efficiently the nanoparticles are homogenized, so that the process can be performed in a shorter time. Generally, mixing and aging are carried out over 1 to 24 hours, particularly about 3 to 10 hours.

After aging, water is removed by evaporative drying using a spray dryer, slurry dryer, etc., but after some dehydration by means such as filtration or centrifugation, a box dryer, band dryer, etc. Drying may be performed using a fluidized layer dryer or the like. At this time, at least a part or all of the hydration of the raw material (B) is eliminated.

As described above, for example, the silica-magnesia composite particles having a water content of 10% by mass or less and in which silicon dioxide (silica) particles, which are raw material particles, and magnesia particles are closely composited by dehydration, are granular. Obtained in the form of powder, cake or baby boom. If necessary, these are pulverized, classified, or molded, and are used as particle shapes suitable for adsorption.
Such silica-magnesia composite particles are commercially available, for example, from Mizusawa Industrial Chemicals Co., Ltd. under the trade name of "Mizuka Life".

<Use as an adsorbent>
The silica-magnesia composite particles obtained as described above have functional components, specifically, lecithin, astaxanthin, quercetin glycoside, chlorogenic acid, isoflavone, linolenic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid. (DHA), catechin derivatives such as catechin and tea catechin, or used for adsorption of gamma oryzanol.

That is, the above-mentioned adsorbent is added to an aqueous solution of the above-mentioned functional component or an alcohol solution such as ethanol obtained in the process of collecting the above-mentioned functional component, and the adsorbent is stirred for an appropriate time to bring the functional component in the liquid. Can be adsorbed.
The above aqueous solution or alcohol solution is not particularly limited in the concentration of the functional component and the amount of the adsorbent used, but is preferably a dilute solution of 5% by mass or less, and usually 0.001 per 100 parts by mass of the solution. An adsorbent of about 25 parts by mass may be used.

After adsorption, filtration can be performed by a known means to isolate the adsorbent on which the functional component is adsorbed.
There is no particular limitation on the method of releasing the adsorbed functional component, and it is carried out by a conventionally known solvent extraction method or the like. For example, it can be put into pure water and subjected to a stirring operation such as ultrasonic vibration to release the adsorbed functional component, and the functional component can be recovered by concentrating or removing the solvent.

The adsorbent of the present invention exhibits particularly excellent adsorptivity to egg yolk lecithin, soybean lecithin, astaxanthin, quercetin glycoside, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and tea catechin.
In addition, when tea catechin is used by blending it with a resin, as described above, it is supported on an inorganic material to prevent coloring or discoloration, or to impart water resistance (water extraction property) to the resin. Although blended, the adsorbent of the present invention has excellent adsorptivity to tea catechin, and therefore can be suitably used as an inorganic material for supporting tea catechin.

The excellent effect of the present invention will be described with reference to the following experimental examples.

(1) Adsorption amount of Orange II The adsorption capacity of Orange II in this example was calculated by measuring and calculating the number of mmol of Orange II capable of adsorbing 1 g of a sample from an aqueous solution of Orange II having a concentration of 10 mmol / L.
First, Orange II (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in water to obtain an orange II aqueous solution having a concentration of 10 mmol / L. Weigh 20 ml of this 10 mmol / L concentration orange II aqueous solution into a 50 ml centrifuge tube, add 0.20 g of test powder, and use a shaker (SA300 manufactured by Yamato Scientific Co., Ltd., shaking speed 5) to 7.5. Shake the time. After shaking, let stand for 12 hours or more. Next, 0.5 mL of the supernatant of the liquid treated with a centrifuge (5200 manufactured by Kubota Co., Ltd.) at a centrifugal acceleration of 3000 rpm for 15 minutes was collected, and this was diluted 200-fold with ion-exchanged water to obtain the absorbance of 484 nm wavelength light. Was measured with a spectrophotometer (V-630 manufactured by JASCO Corporation). Then, the residual amount of Orange II in the sample solution was calculated using a calibration curve showing the relationship between the Orange II content of the Orange II aqueous solution and the absorbance of the 484 nm wavelength light. The value obtained by subtracting this value from the amount of Orange II added to the sample was taken as the amount of Orange II adsorbed.

(2) pH
The adsorbent powder was added to the ion-exchanged water so that the adsorbent concentration was 5% by mass, and the mixture was stirred for 30 minutes, and then measured with a pH meter HM-30R manufactured by Toa DKK.

(3) Adsorption test Using the test solution consisting of the functional component and the solvent shown in Table 1, the adsorption ability for each component was evaluated. The adsorptive capacity was set to an amount (mg) that 1 g of the adsorbent could be adsorbed, measured by the following method, and the calculated values are shown in Table 2.
First, each functional component was dissolved in a solvent to obtain a functional component solution having a concentration of 0.2 g / L. Weigh 30 g of this solution into a centrifuge tube having a capacity of 50 ml, add 1 g of an adsorbent (3.3% by mass with respect to the liquid), and use a horizontal shaker (AS ONE Shaking Bath SB-13) at 150 rpm for 2.5. I shook the time.
Next, a supernatant liquid (sample liquid) of the liquid treated with a centrifuge (CR22GIII manufactured by Hitachi, Ltd.) at a centrifugal acceleration of 18,000 rpm for 20 minutes was obtained. The absorbance of the sample solution was measured with a spectrophotometer (SPECTROPHOTOMETER UV-3600 manufactured by Shimadzu Corporation). At this time, if there is an influence of leaching and desalting of the test powder, the absorbance when the test powder is added to the solvent in which each component is undissolved in advance and the same operation is performed is subtracted from the absorbance of the sample solution, and the corrected absorbance of the sample solution is subtracted. And said. Then, the residual amount of the component of the sample solution was calculated using a calibration curve showing the relationship between the component concentration and the absorbance prepared in advance, and the value subtracted from the amount of the component before the addition of the adsorbent was taken as the component adsorption amount of the adsorbent. All tests were repeated 2 times and the average value was used.

Table 2 shows the results of the adsorption test for the adsorbent powders shown in the following Examples and Comparative Examples.

(Comparative Example 1)
Mizusawa Industrial Chemicals Co., Ltd.'s Acid Clay Mizuka Ace No. 20 (pH 4.9).

(Comparative Example 2)
220 ml of a 5 mass% sulfuric acid aqueous solution was placed in a beaker and heated to 90 ° C. 30 g of the acidic clay of Comparative Example 1 was added thereto, and the mixture was stirred while the liquid temperature was maintained at 90 ° C., and acid treatment was performed for 30 minutes. After completion of the acid treatment, the acid-treated product was filtered and washed with water, and the washed filtered cake was dried at 110 ° C., pulverized and classified to obtain a weak acid-treated white clay powder (pH 3.1).

(Comparative Example 3)
Silicon dioxide Mizuka Sorb C-6 (pH 6.5) manufactured by Mizusawa Industrial Chemicals Co., Ltd.

(Example 1)
Mizusawa Industrial Chemicals Co., Ltd.'s composite adsorbent Mizuka Life F-2G (pH 8.9, R = 1.9, anion adsorption capacity 55 mmol / 100 g) containing silicon dioxide and magnesium oxide as main components is used as silica particles and magnesia particles. It was used as a silica-magnesia composite particle integrally composited with.

(Comparative Example 4)
Activated clay galleon earth V2 (pH 3.5) manufactured by Mizusawa Industrial Chemicals Co., Ltd.

Claims (2)

Adsorption of functional components selected from the group consisting of lecithin, astaxanthin, quercetin glycosides, chlorogenic acid, isoflavones, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), catechin and its derivatives, and gamma oryzanol. It is an adsorbent used in the above, and is composed of silica-magnesia composite particles in which silica particles and magnesia particles are integrally composited, and the anion adsorbing ability represented by the amount of Orange II adsorbed is in the range of 18 to 74 mmol / 100 g. Characteristic adsorbent. The silica component and the magnesia component are expressed by the following formula (1):
R = Sm / Mm (1)
In the formula, Sm is the content (mass%) of the silica component in terms of _{SiO 2.}
Mm is the content (mass%) of the magnesia component in terms of MgO.
The adsorbent according to claim 1, wherein the mass ratio (R) represented by is contained in a ratio of 0.1 ≦ R ≦ 3.5.