JP2013000156A - Fiber composite for application of liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a convenient means that provides an antioxidative property for a liquid (e.g., skin toner) when a user uses it.SOLUTION: Fiber composite for the application of a liquid includes a fibrous member containing a porous carbon material having a specific surface area value by the nitrogen BET method of ≥10 m/g, and a pore volume by the BJH method and MP method of ≥0.2 cm/g preferably ≥0.4 cm/g.

Description

  The present disclosure relates to a fiber composite for liquid application.

  In recent years, water showing reductive properties such as alkaline ionized water, electrolytically reduced water, and hydrogen water has attracted attention from the viewpoint of maintaining human health (for example, JP2003-301288, JP2002-348208, JP, 2001-314877, A). In addition, oxidative stress substances such as oxygen radical species, which are active oxygen species in a broad sense, such as superoxide radicals, hydroxyl radicals, hydrogen peroxide, singlet oxygen, nitric oxide, and lipid peroxide, cause various diseases and aging. In recent years, it has been proven by the medical society. And it is said that removing such an oxidative stress substance by causing an antioxidative cosmetic material to act on the skin is very useful in preventing various diseases and aging.

JP2003-301288 JP2002-348208 JP 2001-314877 A

  By the way, as far as the present inventors have investigated, there is no known simple method or means for imparting antioxidative properties to liquids such as cosmetics.

  Therefore, an object of the present disclosure is to provide a simple means for imparting antioxidant properties to a liquid (for example, lotion) when used by a user.

The fiber composite for coating liquid according to the first aspect of the present disclosure for achieving the above object has a specific surface area value of 10 m ² / gram or more according to the nitrogen BET method and a pore volume of 0. It consists of a fibrous member containing a porous carbon material of 2 cm ³ / gram or more, preferably 0.4 cm ³ / gram or more.

The fiber composite for liquid application according to the second aspect of the present disclosure for achieving the above object has a specific surface area value of 10 m ² / gram or more determined by a nitrogen BET method by a delocalized density functional method. A porous carbon material having a total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m is 0.5 cm ³ / gram or more, preferably 1.0 cm ³ / gram or more. It consists of a fibrous member.

The fiber composite for liquid application according to the third aspect of the present disclosure for achieving the above object has a specific surface area value of 10 m ² / gram or more determined by a nitrogen BET method, and is determined by a delocalized density functional method. In the obtained pore size distribution, the proportion of the total volume of pores having at least one peak in the range of 3 nm to 20 nm and having a pore size in the range of 3 nm to 20 nm is the total volume of all pores. It consists of the fibrous member containing the porous carbon material which is 0.2 or more.

  In the fiber composite for liquid application according to the first to third aspects of the present disclosure, the specific surface area, pore volume, and pore distribution of the porous carbon material according to the nitrogen BET method are defined. Therefore, it is possible to easily impart anti-oxidant properties to liquids (for example, lotions) that reliably remove oxidative stress substances contained in liquids and that reliably reduce the redox potential of liquids. Can do. In addition, since liquid (for example, skin lotion, etc.) may be used by soaking into the fibrous member, characteristics such as antioxidant properties can be imparted to the liquid by very simple means and methods. In general, an oxidative stress substance is easy to receive electrons (that is, the standard oxidation-reduction potential is high in the positive direction). Therefore, when the oxidative stress substance is removed, the ease of receiving electrons decreases (giving electrons). Ease increases). That is, the redox potential increases in the negative direction.

FIG. 1 is a graph in which the relationship between the addition amount of the porous carbon material of Example 1 and the activated carbon of Comparative Example 1 and pH is examined. FIG. 2 is a graph in which the relationship between the addition amount of the porous carbon material of Example 1 and the activated carbon of Comparative Example 1 and the oxidation-reduction potential is examined.

Hereinafter, although this indication is explained based on an example with reference to drawings, this indication is not limited to an example and various numerical values and materials in an example are illustrations. The description will be given in the following order.
1. 1. General description of the fiber composite for liquid application according to the first to third aspects of the present disclosure. Example 1 (Liquid composite for liquid application according to first to third aspects of the present disclosure), others

[Description of General for Fiber Composite for Liquid Application According to First to Third Aspects of Present Disclosure]
In the fiber composite for liquid application according to the first to third aspects of the present disclosure, the porous carbon material may have a functional material attached thereto. Such a form may be referred to as a “porous carbon material composite” for convenience.

  In the fiber composite for applying a liquid according to the first to third aspects of the present disclosure including the above preferred forms, the liquid is contained in the fibrous member and the liquid is applied (usage form). It can be. And in such a usage form, the oxidative stress substance contained in the liquid can be removed by bringing the liquid into contact with the porous carbon material, or the liquid is brought into contact with the porous carbon material. Can reduce the oxidation-reduction potential of the liquid. That is, characteristics such as antioxidant properties can be imparted to the liquid.

  Here, water can be exemplified as the liquid, but is not limited thereto, and examples thereof include cleansing agents that remove dirt components such as lotion, milky lotion, sweat, fats and oils, and lipstick.

  Examples of the oxidative stress substance include hydroxyl radical, singlet oxygen, superoxide radical, hydrogen peroxide, nitric oxide, and lipid peroxide. Oxidative stress substances (hydroxyl radicals, singlet oxygen, superoxide radicals, hydrogen peroxide, nitric oxide, lipid peroxide, etc., which are reactive oxygen species) exist when oxidative stress substances contained in a liquid are removed. This means that the oxidative stress substance is reduced by the porous carbon material and the oxidative stress substance is changed to water molecules or oxygen molecules.

  Alternatively, it reduces the oxidation-reduction potential of the liquid. Here, chlorine, trihalomethane, oxidative stress substances (reactive oxygen species such as hydroxyl radical, singlet oxygen, superoxide radical, hydrogen peroxide, nitric oxide, hydrogen peroxide, These substances are removed from the oxidized state due to the inclusion of lipid oxides, etc.), and mineral components (considered as residual ash generated in the firing and activation processes contained on the surface and inside of the porous carbon material) are eluted. Assume that when the state is reached, the redox potential of the liquid is lowered. That is, since chlorine, trihalomethane, and oxidative stress substances have a high redox potential (ie, high acidity), they are removed by adsorption or reduction reaction with porous carbon materials and strong alkalis from porous carbon materials. It is considered that the elution of weak acid salt (potassium carbonate or the like) contributes to the reduction of the redox potential. The oxidation-reduction potential of the liquid can be measured by using a tripolar electrometer using an Ag / AgCl electrode as a reference electrode. In addition, it is desirable that the redox potential of the liquid after being lowered is 150 millivolts or less.

  In the fiber composite for liquid application according to the first to third aspects of the present disclosure including the preferred embodiments described above, the raw material of the porous carbon material is a plant-derived material containing silicon (Si). In this case, although not specifically limited, the porous carbon material is made from a plant-derived material having a silicon (Si) content of 5% by mass or more as a raw material. The content of silicon (Si) in the carbon material is desirably 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less.

  In some cases, the fiber composites for liquid application according to the first to third aspects of the present disclosure including the preferred embodiments described above (hereinafter collectively referred to simply as “for liquid application of the present disclosure”). Porous carbon material (hereinafter may be referred to simply as “porous carbon material etc. of the present disclosure”) or a porous carbon material constituting “fiber composite etc.”) The surface of the composite may be subjected to hydrophilic treatment or hydrophobic treatment.

  In the fiber composite for coating liquid and the like of the present disclosure, the porous carbon material of the present disclosure, for example, due to a small amount of elution of carbonate generated in the carbonization and activation process, By increasing the ash content by increasing the degree of activation in the carbonaceous material or the like, the liquid can be made alkaline or the pH value can be increased. Moreover, it can be made acidic by generating a carboxy group (achievable by nitric acid treatment) or a sulfone group (achievable by concentrated sulfuric acid) on the surface of the porous carbon material or the like of the present disclosure. It can also be reduced. Alternatively, a reducing agent such as hydrogen can be included in the liquid. In addition, the liquid structure (cluster) can be changed by passing through a fine structure such as the porous carbon material of the present disclosure.

  In the fiber composite for liquid application and the like of the present disclosure, the fibrous member includes a porous carbon material. As a specific configuration of the fiber composite for liquid application and the like of the present disclosure, the porous material of the present disclosure A structure in which a carbon material or the like is previously kneaded into a fiber constituting the fibrous member, spun, and subjected to a crimping process such as mechanical crimping or coil crimping as necessary to form a woven or non-woven fabric can be exemplified. In addition, the structure based on these woven fabrics or non-woven fabrics can be mentioned, the porous carbon material of the present disclosure can be attached to the fibrous member using a binder, etc. For example, the disclosed porous carbon material can be formed into a desired shape using a binder (binder) or the like, and sandwiched between layered fibrous members. Combined as appropriate Rukoto can also. Specific product forms of the fiber composite for liquid application of the present disclosure may include, for example, a cosmetic cotton, a cosmetic putting material, a cosmetic puff, a cosmetic cut cotton, and a disinfecting puff.

  Natural materials such as cotton, hemp, bamboo, wool, and pulp; cellulose-based recycled fibers; polypropylene, polyester, nylon, vinylon, polyethylene, polyamide, aromatic polyamide, polyolefin, polystyrene, acrylic Woven fabrics and non-woven fabrics made of at least one synthetic fiber such as rayon, polyvinyl alcohol, polytetrafluoroethylene, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, etc. Well-known cloth materials such as woven fabrics and nonwoven fabrics, cloth-like materials, gauze-like materials, and the like can be mentioned, and carboxynitrocellulose can be mentioned as a binder. In addition, examples of the form of the synthetic fiber include a core-sheath type, an eccentric core-sheath type, a multi-layer bonding type, a side-by-side type, and the like, and the cross-sectional shape can be not only a circular shape but also an irregular cross-sectional shape.

  The porous carbon material of the present disclosure can be obtained, for example, by carbonizing a plant-derived material at 400 ° C. to 1400 ° C. and then treating with an acid or an alkali. In such a method for producing a porous carbon material or the like in the present disclosure (hereinafter sometimes simply referred to as “a method for producing a porous carbon material”), the plant-derived material is heated at 400 ° C. to 1400 ° C. A material obtained by carbonization before being treated with an acid or alkali is called a “porous carbon material precursor” or a “carbonaceous substance”.

  In the manufacturing method of a porous carbon material, the process of performing an activation process can be included after the process with an acid or an alkali, and after performing an activation process, you may perform the process with an acid or an alkali. Further, in the method for producing a porous carbon material including such a preferable form, depending on the plant-derived material to be used, before carbonizing the plant-derived material, the temperature for carbonization is determined. Alternatively, the plant-derived material may be subjected to a heat treatment (preliminary carbonization treatment) at a low temperature (for example, 400 ° C. to 700 ° C.) in a state where oxygen is blocked. As a result, the tar component that will be generated in the carbonization process can be extracted. As a result, the tar component that will be generated in the carbonization process can be reduced or eliminated. The state in which oxygen is shut off is, for example, an inert gas atmosphere such as nitrogen gas or argon gas, or a vacuum atmosphere, or a plant-derived material is in a kind of steamed state. Can be achieved. Moreover, in the method for producing a porous carbon material, depending on the plant-derived material to be used, in order to reduce mineral components and moisture contained in the plant-derived material, and in the process of carbonization. In order to prevent the generation of the off-flavor, the plant-derived material may be immersed in alcohol (for example, methyl alcohol, ethyl alcohol, isopropyl alcohol). In addition, in the manufacturing method of a porous carbon material, you may perform a preliminary carbonization process after that. As a material that is preferably heat-treated in an inert gas, for example, a plant that generates a large amount of wood vinegar liquid (tar or light oil) can be mentioned. In addition, examples of materials that are preferably pretreated with alcohol include seaweeds that contain a large amount of iodine and various minerals.

  In the method for producing a porous carbon material, a plant-derived material is carbonized at 400 ° C. to 1400 ° C. Here, carbonization is generally an organic substance (the porous carbon of the present disclosure). In the case of materials and the like, it means that a plant-derived material is heat-treated to convert it into a carbonaceous substance (for example, see JIS M0104-1984). The atmosphere for carbonization can include an atmosphere in which oxygen is shut off. Specifically, a vacuum atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas, and a plant-derived material as a kind of steamed state. The atmosphere to do can be mentioned. The rate of temperature rise until reaching the carbonization temperature is not limited, but in such an atmosphere, 1 ° C / min or more, preferably 3 ° C / min or more, more preferably 5 ° C / min or more. be able to. The upper limit of the carbonization time can be 10 hours, preferably 7 hours, more preferably 5 hours, but is not limited thereto. The lower limit of the carbonization time may be a time during which the plant-derived material is reliably carbonized. Moreover, the plant-derived material may be pulverized as desired to obtain a desired particle size, or may be classified. Plant-derived materials may be washed in advance. Alternatively, the obtained porous carbon material precursor or porous carbon material may be pulverized as desired to obtain a desired particle size or classified. Alternatively, the porous carbon material after the activation treatment may be pulverized as desired to obtain a desired particle size or may be classified. Further, the porous carbon material finally obtained may be sterilized. There is no restriction | limiting in the form, structure, and structure of the furnace used for carbonization, It can also be set as a continuous furnace and can also be set as a batch furnace (batch furnace).

  In the production of the porous carbon material composite, after obtaining the porous carbon material by treating with an acid or alkali, a functional material may be attached to the porous carbon material. Moreover, the process of performing an activation process can be included after making the functional material adhere to a porous carbon material after the process with an acid or an alkali. Here, as the functional material, for example, platinum (Pt), or platinum (Pt) and palladium (Pd) can be cited. As the form of adhesion of the functional material to the porous carbon material, the state of fine particles Adhesion in a thin film or in a thin film state can be exemplified. Specifically, it adheres as a fine particle or in a thin film state on the surface of a porous carbon material (including the inside of pores). And a state of adhering to the sea / island state (when the surface of the porous carbon material is regarded as “the sea”, the functional material corresponds to “the island”). Adhesion refers to an adhesion phenomenon between different kinds of materials. As a method of attaching the functional material to the porous carbon material, the method of depositing the functional material on the surface of the porous carbon material by immersing the porous carbon material in a solution containing the functional material, the surface of the porous carbon material Porous material by electroless plating method (chemical plating method) or method of depositing functional material by chemical reduction reaction, by immersing porous carbon material in solution containing functional material precursor and performing heat treatment A method of depositing a functional material on the surface of the carbon material, a functional material on the surface of the porous carbon material by immersing the porous carbon material in a solution containing a precursor of the functional material and performing ultrasonic irradiation treatment And a method of precipitating the functional material on the surface of the porous carbon material by immersing the porous carbon material in a solution containing the functional material precursor and performing a sol-gel reaction. so That.

  In the method for producing a porous carbon material, as described above, when the activation treatment is performed, micropores (described later) having a pore diameter smaller than 2 nm can be increased. Examples of the activation treatment method include a gas activation method and a chemical activation method. Here, the gas activation method uses oxygen, water vapor, carbon dioxide gas, air or the like as an activator, and in such a gas atmosphere, at 700 ° C. to 1400 ° C., preferably at 700 ° C. to 1000 ° C. More preferably, by heating the porous carbon material at 800 ° C. to 1000 ° C. for several tens of minutes to several hours, the microstructure is developed by the volatile components and carbon molecules in the porous carbon material. is there. More specifically, the heating temperature may be appropriately selected based on the type of plant-derived material, the type and concentration of gas, and the like. The chemical activation method is activated with zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, sulfuric acid, etc. instead of oxygen and water vapor used in the gas activation method, washed with hydrochloric acid, alkaline In this method, the pH is adjusted with an aqueous solution and dried.

  Chemical treatment or molecular modification may be performed on the surface of the porous carbon material or the like of the present disclosure. Examples of the chemical treatment include a treatment for generating a carboxy group on the surface by nitric acid treatment. Moreover, various functional groups, such as a hydroxyl group, a carboxy group, a ketone group, an ester group, can also be produced | generated on the surface of a porous carbon material by performing the process similar to the activation process by water vapor | steam, oxygen, an alkali. Furthermore, molecular modification can also be achieved by chemically reacting a chemical species or protein having a hydroxyl group, a carboxy group, an amino group or the like that can react with the porous carbon material.

In the method for producing a porous carbon material, the silicon component in the plant-derived material after carbonization is removed by treatment with acid or alkali. Here, examples of the silicon component include silicon oxides such as silicon dioxide, silicon oxide, and silicon oxide salts. Thus, the porous carbon material which has a high specific surface area can be obtained by removing the silicon component in the plant-derived material after carbonization. In some cases, the silicon component in the plant-derived material after carbonization may be removed based on a dry etching method. That is, in a preferred form of the porous carbon material and the like of the present disclosure, a plant-derived material containing silicon (Si) is used as a raw material, but when converted into a porous carbon material precursor or a carbonaceous material. By carbonizing a plant-derived material at a high temperature (for example, 400 ° C. to 1400 ° C.), silicon contained in the plant-derived material does not become silicon carbide (SiC), but silicon dioxide. It becomes a silicon component (silicon oxide) such as (SiO _x ), silicon oxide, or silicon oxide salt. In addition, even if the silicon component (silicon oxide) contained in the plant-derived material before carbonization is carbonized at a high temperature (for example, 400 ° C to 1400 ° C), a substantial change occurs. Absent. Therefore, by treating with an acid or alkali (base) in the next step, silicon components (silicon oxide) such as silicon dioxide, silicon oxide, and silicon oxide salt are removed, resulting in a large specific surface area by nitrogen BET method. A value can be obtained. In addition, in a preferred form of the porous carbon material and the like of the present disclosure, it is an environmentally compatible material derived from a natural product, and its microstructure is a silicon component (silicon oxide) previously contained in a raw material that is a plant-derived material. Is obtained by treating with acid or alkali and removing the product. Therefore, the pore arrangement maintains the bioregularity of the plant.

  As described above, the porous carbon material can be made from a plant-derived material. Here, as plant-derived materials, rice husks and straws such as rice (rice), barley, wheat, rye, rice husk and millet, rice beans, tea leaves (for example, leaves such as green tea and tea), Citrus such as sugar cane (more specifically, sugar cane squeezed straw), corn (more specifically, corn core), fruit peel (eg orange peel, grapefruit peel, mandarin peel) But also, but not limited to, vascular plants, fern plants, moss plants, algae Can mention seaweed. In addition, these materials may be used independently as a raw material, and multiple types may be mixed and used. Further, the shape and form of the plant-derived material are not particularly limited, and may be, for example, rice husk or straw itself, or may be a dried product. Furthermore, what processed various processes, such as a fermentation process, a roasting process, an extraction process, can also be used in food-drinks processing, such as beer and western liquor. In particular, it is preferable to use straws and rice husks after processing such as threshing from the viewpoint of recycling industrial waste. These processed straws and rice husks can be easily obtained in large quantities from, for example, agricultural cooperatives, liquor manufacturers, food companies, and food processing companies.

  The porous carbon material of the present disclosure includes non-metallic elements such as magnesium (Mg), potassium (K), calcium (Ca), phosphorus (P), and sulfur (S), and metal elements such as transition elements. It may be included. Magnesium (Mg) content of 0.01% by mass to 3% by mass, potassium (K) content of 0.01% by mass to 3% by mass, calcium (Ca) content of 0.05% by mass % To 3% by mass, phosphorus (P) content of 0.01% to 3% by mass, and sulfur (S) content of 0.01% to 3% by mass. The content of these elements is preferably smaller from the viewpoint of increasing the specific surface area. Needless to say, the porous carbon material may contain elements other than the above-described elements, and the range of the content of each of the above-mentioned various elements can be changed.

  In the present disclosure, analysis of various elements can be performed by an energy dispersion method (EDS) using, for example, an energy dispersive X-ray analyzer (for example, JED-2200F manufactured by JEOL Ltd.). Here, the measurement conditions may be, for example, a scanning voltage of 15 kV and an irradiation current of 10 μA.

The porous carbon material of the present disclosure has many pores. The pores include “mesopores” having a pore diameter of 2 nm to 50 nm, “micropores” having a pore diameter smaller than 2 nm, and “macropores” having a pore diameter exceeding 50 nm. Specifically, the mesopores include, for example, many pores having a pore diameter of 20 nm or less, and particularly many pores having a pore diameter of 10 nm or less. The micropores include, for example, many pores having a pore diameter of about 1.9 nm, pores of about 1.5 nm, and pores of about 0.8 nm to 1 nm. In the present disclosure of the porous carbon material or the like, it is preferable that the pore volume of at 0.2 cm ³ / g or more determined by the BJH method, more preferably at 0.4 cm ³ / g or more, 0.6 cm ³ / It is even more preferable that it is gram or more.

In the porous carbon material and the like of the present disclosure, the specific surface area value by the nitrogen BET method (hereinafter sometimes simply referred to as “specific surface area value”) is preferably in order to obtain even more excellent functionality. It is desirable that it is 50 m ² / gram or more, more preferably 100 m ² / gram or more, and still more preferably 400 m ² / gram or more.

The nitrogen BET method is an adsorption isotherm measured by adsorbing and desorbing nitrogen as an adsorbed molecule on an adsorbent (here, a porous carbon material), and the measured data is converted into a BET equation represented by equation (1). Based on this method, the specific surface area, pore volume, and the like can be calculated. Specifically, when calculating the value of the specific surface area by the nitrogen BET method, first, an adsorption isotherm is obtained by adsorbing and desorbing nitrogen as an adsorbed molecule on the porous carbon material. Then, [p / {V _a (p ₀ −p)}] is calculated from the obtained adsorption isotherm based on the formula (1) or the formula (1 ′) obtained by modifying the formula (1), and the equilibrium relative pressure is calculated. Plot against (p / p ₀ ). Then, this plot is regarded as a straight line, and based on the least square method, the slope s (= [(C-1) / (C · V _m )]) and the intercept i (= [1 / (C · V _m )]) Is calculated. Then, V _m and C are calculated from the obtained slope s and intercept i based on the equations (2-1) and (2-2). Furthermore, the specific surface area a _sBET is calculated from V _m based on the formula (3) (see BELSORP-mini and BELSORP analysis software manual, pages 62 to 66, manufactured by Bell Japan Co., Ltd.). The nitrogen BET method is a measurement method according to JIS R 1626-1996 “Measurement method of specific surface area of fine ceramic powder by gas adsorption BET method”.

_{V a = (V m · C} · p) / [(p 0 -p) {1+ (C-1) (p / p 0)}] (1)
[P / {V _a (p ₀ −p)}]
= [(C-1) / (C · V _m )] (p / p ₀ ) + [1 / (C · V _m )] (1 ′)
V _m = 1 / (s + i) (2-1)
C = (s / i) +1 (2-2)
_{a sBET = (V m · L} · σ) / 22414 (3)

However,
V _a : Adsorption amount V _m : Adsorption amount of monolayer p: Nitrogen equilibrium pressure p ₀ : Nitrogen saturated vapor pressure L: Avogadro number σ: Nitrogen adsorption cross section.

When the pore volume V _p is calculated by the nitrogen BET method, for example, the adsorption data of the obtained adsorption isotherm is linearly interpolated to obtain the adsorption amount V at the relative pressure set by the pore volume calculation relative pressure. The pore volume V _p can be calculated from this adsorption amount V based on the formula (4) (see BELSORP-mini and BELSORP analysis software manual, page 62 to page 65, manufactured by Bell Japan Co., Ltd.). Hereinafter, the pore volume based on the nitrogen BET method may be simply referred to as “pore volume”.

V _p = (V / 22414) × (M _g / ρ _g ) (4)

However,
V: Adsorption amount at relative pressure M _g : Nitrogen molecular weight ρ _g : Nitrogen density.

The pore diameter of the mesopores can be calculated as a pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the BJH method. The BJH method is widely used as a pore distribution analysis method. When pore distribution analysis is performed based on the BJH method, first, desorption isotherms are obtained by adsorbing and desorbing nitrogen as adsorbed molecules on the porous carbon material. Then, based on the obtained desorption isotherm, the thickness of the adsorption layer when the adsorption molecules are attached and detached in stages from the state where the pores are filled with the adsorption molecules (for example, nitrogen), and the pores generated at that time obtains an inner diameter (twice the core radius) of calculating the pore radius r _p based on equation (5) to calculate the pore volume based on the equation (6). Then, the pore radius and the pore volume variation rate relative to the pore diameter (2r _p) from the pore volume (dV _p / dr _p) pore distribution curve is obtained by plotting the (BEL Japan Ltd. BELSORP-mini And BELSORP analysis software manual, pages 85-88).

r _p = t + r _k (5)
V _pn = R _n · dV _n -R _n · dt _n · c · ΣA _pj (6)
However,
R _n = r _pn ² / (r _kn −1 + dt _n ) ² (7)

here,
r _p : pore radius r _k : core radius (inner diameter / 2) when the adsorption layer having a thickness t is adsorbed on the inner wall of the pore having the pore radius r _p at that pressure
V _pn : pore volume dV _n when the nth attachment / detachment of nitrogen occurs: change amount dt _{n at} that time: change in the thickness t _n of the adsorption layer when the nth attachment / detachment of nitrogen occurs Amount r _kn : Core radius c at that time c: Fixed value r _pn : Pore radius when the nth attachment / detachment of nitrogen occurs. ΣA _pj represents the integrated value of the area of the wall surfaces of the pores from j = 1 to j = n−1.

  The pore diameter of the micropores can be calculated as a pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the MP method. When performing pore distribution analysis by the MP method, first, an adsorption isotherm is obtained by adsorbing nitrogen to a porous carbon material. Then, this adsorption isotherm is converted into a pore volume with respect to the thickness t of the adsorption layer (t plotted). A pore distribution curve can be obtained based on the curvature of this plot (the amount of change in pore volume with respect to the amount of change in the thickness t of the adsorption layer) (BELSORP-mini and BELSORP analysis software manuals manufactured by Bell Japan Co., Ltd.). 72 to 73 and 82).

  JIS Z8831-2: 2010 “Pore size distribution and pore characteristics of powder (solid) —Part 2: Method for measuring mesopores and macropores by gas adsorption” and JIS Z8831-3: 2010 “Powder” Pore size distribution and pore properties of solid bodies (solid)-Part 3: Nonlocalized density functional theory method (NLDFT method, Non Localized Density Functional Theory method) In that case, software attached to an automatic specific surface area / pore distribution measuring device “BELSORP-MAX” manufactured by Bell Japan Co., Ltd. is used as analysis software. As a precondition, the model is assumed to be a cylinder shape and carbon black (CB) is assumed, the distribution function of the pore distribution parameter is “no-assumtion”, and the obtained distribution data is smoothed 10 times.

The porous carbon material precursor is treated with an acid or alkali. Specific treatment methods include, for example, a method of immersing the porous carbon material precursor in an acid or alkali aqueous solution, or a porous carbon material precursor and an acid. Or the method of making it react with an alkali by a gaseous phase can be mentioned. More specifically, when treating with an acid, examples of the acid include fluorine compounds exhibiting acidity such as hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, and sodium fluoride. When a fluorine compound is used, it is sufficient that the amount of fluorine element is 4 times the amount of silicon element in the silicon component contained in the porous carbon material precursor, and the concentration of the fluorine compound aqueous solution is preferably 10% by mass or more. When the silicon component (for example, silicon dioxide) contained in the porous carbon material precursor is removed by hydrofluoric acid, the silicon dioxide is mixed with hydrofluoric acid as shown in chemical formula (A) or chemical formula (B). It reacts and is removed as hexafluorosilicic acid (H ₂ SiF ₆ ) or silicon tetrafluoride (SiF ₄ ) to obtain a porous carbon material. Thereafter, washing and drying may be performed.

SiO ₂ + 6HF → H ₂ SiF ₆ + 2H ₂ O (A)
SiO ₂ + 4HF → SiF ₄ + 2H ₂ O (B)

Moreover, when processing with an alkali (base), sodium hydroxide can be mentioned as an alkali, for example. When an alkaline aqueous solution is used, the pH of the aqueous solution may be 11 or more. When the silicon component (for example, silicon dioxide) contained in the porous carbon material precursor is removed with the aqueous sodium hydroxide solution, the silicon dioxide is heated as shown in the chemical formula (C) by heating the aqueous sodium hydroxide solution. It reacts and is removed as sodium silicate (Na ₂ SiO ₃ ) to obtain a porous carbon material. In addition, when processing by reacting sodium hydroxide in the gas phase, the sodium hydroxide solid is heated to react as shown in the chemical formula (C) and is removed as sodium silicate (Na ₂ SiO ₃ ). A porous carbon material can be obtained. Thereafter, washing and drying may be performed.

SiO ₂ + 2NaOH → Na ₂ SiO ₃ + H ₂ O (C)

Alternatively, as a porous carbon material or the like in the present disclosure, for example, a porous carbon material in which pores disclosed in JP 2010-106007 have a three-dimensional regularity (a so-called porous carbon material having an inverse opal structure) ), Specifically, three-dimensionally arranged spherical pores having an average diameter of 1 × 10 ⁻⁹ m to 1 × 10 ⁻⁵ m, and a surface area of 3 × 10 ² m ² / gram or more Porous carbon material, preferably, macroscopically, pores are arranged in an arrangement state corresponding to a crystal structure, or macroscopically corresponds to (111) plane orientation in a face-centered cubic structure It is also possible to use a porous carbon material in which pores are arranged on the surface in the arrangement state.

  Example 1 relates to a fiber composite for liquid application according to the first to third aspects of the present disclosure.

The liquid coating fiber composite of Example 1 is expressed in accordance with the liquid coating fiber composite according to the first aspect of the present disclosure. The specific surface area value by the nitrogen BET method is 10 m ² / gram or more, and the BJH method. It comprises a fibrous member containing a porous carbon material having a pore volume of 0.2 cm ³ / gram or more, preferably 0.4 cm ³ / gram or more, more preferably 0.6 cm ³ / gram or more. Moreover, when expressed in accordance with the fiber composite for liquid application according to the second aspect of the present disclosure, the value of the specific surface area by the nitrogen BET method is 10 m ² / gram or more, and the delocalized density functional method (NLDFT method) The total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m (referred to as “volume A” for convenience) determined by the above is 0.5 cm ³ / gram or more, preferably 1.0 cm ³ It consists of a fibrous member containing a porous carbon material that is at least / gram. Furthermore, when expressed in accordance with the fiber composite for liquid application according to the third aspect of the present disclosure, the value of the specific surface area by the nitrogen BET method is 10 m ² / gram or more, which is obtained by the delocalized density functional method. In the pore size distribution, the ratio of the total volume of pores having at least one peak in the range of 3 nm to 20 nm and having a pore size in the range of 3 nm to 20 nm is the total volume of all pores (volume (Corresponding to A) of 0.2 or more, preferably 0.4 or more, a fibrous member containing a porous carbon material.

  In Example 1, the fiber composite for liquid application has a form such as cosmetic cotton. The fibrous member is made of a non-woven fabric made of cotton and has a rectangular planar shape. Specifically, based on a well-known method, the fiber composite for Example 1 can be obtained by kneading into fibers (cotton) constituting the fibrous member in advance, spinning, and forming a nonwoven fabric. .

  And in Example 1, a liquid is included in a fibrous member and a liquid is apply | coated. More specifically, a liquid such as a well-known skin lotion is contained in a fibrous member, and the liquid member (skin lotion) is applied to the skin of the user's face, arms, limbs, etc. Apply and adhere. Here, the oxidative stress substance contained in the liquid (skin lotion) is removed by contacting the liquid (skin lotion) with the porous carbon material, or the liquid (skin lotion) is contacted with the porous carbon material. To lower the redox potential of the liquid (skin lotion). That is, a property such as antioxidant properties is imparted to the liquid (skin lotion).

  In Example 1, rice (rice) rice husk was used as the plant-derived material that is the raw material of the porous carbon material. And the porous carbon material in Example 1 is obtained by carbonizing the chaff as a raw material, converting it into a carbonaceous substance (porous carbon material precursor), and then performing an acid treatment. Hereinafter, the manufacturing method of the porous carbon material in Example 1 is demonstrated.

  In the production of the porous carbon material in Example 1, a plant-derived material (silicon content: about 20% by mass) is carbonized at 400 ° C. to 1400 ° C. and then treated with an acid or an alkali. Thus, a porous carbon material was obtained. That is, first, heat treatment (preliminary carbonization treatment) is performed on the rice husk in an inert gas. Specifically, the rice husk was carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain a carbide. In addition, by performing such a process, the tar component which will be produced | generated at the time of the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was put in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonized at 800 degreeC for 1 hour, after converting into a carbonaceous substance (porous carbon material precursor), it cooled to room temperature. In addition, nitrogen gas was continued to flow during carbonization and cooling. Next, this porous carbon material precursor was subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed with water and ethyl alcohol until pH 7 was reached. Next, after drying at 120 ° C., the activation treatment was performed by heating at 900 ° C. in a steam stream (5 liters / minute) for 3 hours, so that the porous carbon material of Example 1 (silicon Content: about 0.5% by mass).

  As Comparative Example 1, activated carbon manufactured by Wako Pure Chemical Industries, Ltd. was used.

A nitrogen adsorption / desorption test was performed using BELSORP-mini (manufactured by Nippon Bell Co., Ltd.) as a measuring instrument for determining the specific surface area and pore volume. As measurement conditions, the measurement equilibrium relative pressure (p / p ₀ ) was set to 0.01 to 0.99. The specific surface area and pore volume were calculated based on BELSORP analysis software. In addition, the pore size distribution of mesopores and micropores was calculated based on the BJH method and the MP method using BELSORP analysis software after performing a nitrogen adsorption / desorption test using the above-described measuring instrument. The pores of the porous carbon material were measured by a mercury intrusion method. Specifically, mercury porosimetry was performed using a mercury porosimeter (PASCAL 440: manufactured by Thermo Electron). The pore measurement region was 10 μm to 2 nm. Furthermore, in the measurement based on the delocalized density functional method (NLDFT method), an automatic specific surface area / pore distribution measuring device “BELSORP-MAX” manufactured by Nippon Bell Co., Ltd. was used. In the measurement, the sample was dried at 200 ° C. for 3 hours as a pretreatment.

When the specific surface area and the pore volume were measured for the porous carbon material of Example 1, the porous carbon material composite of Example 2 described later, and the activated carbon of Comparative Example 1, the results shown in Table 1 were obtained. It was. In Table 1, “specific surface area” refers to the value of the specific surface area by the nitrogen BET method, and the unit is m ² / gram. The “MP method”, “BJH method”, and “mercury intrusion method” are the results of volume measurement of pores (micropores) by the MP method, and the volume of pores (mesopores to macropores) by the BJH method. The measurement results and the volume measurement results of the pores by the mercury intrusion method are shown, and the unit is cm ³ / gram. Furthermore, Table 2 shows the results of measurement based on the NLDFT method. Note that the value of the total volume of all pores corresponds to the value of the volume A described above.

[Table 1]
Specific surface area BJH method MP method Mercury intrusion method Example 1 1700 1.08 0.60 4.12
Example 2 1286 0.65 0.50
Comparative Example 1 982 0.08 0.38 1.10

[Table 2]
Volume ratio Total volume of all pores (volume A)
Example 1 0.479 1.33 cm < ³ > / gram Example 2 0.432 1.38 cm < ³ > / gram Comparative Example 1 0.125 0.40 cm < ³ > / gram

  The removal amount of hydroxyl radicals (OH.) In water of the porous carbon material of Example 1, the porous carbon material composite of Example 2, and the activated carbon of Comparative Example 1 was measured with an electron spin resonance apparatus (ESR). It was measured. Specifically, 15 milligrams of sample was added to 50 milliliters of hydroxyl radical generating aqueous solution and stirred for 1 minute, and then the solution was measured by ESR. As a result, the relative removal amount of hydroxyl radicals when Comparative Example 1 was set to “1” was 3.2 in Example 1. In Example 2 described later, it was 7.4.

  In addition, the measurement results of the pH and redox potential of water when using the porous carbon material of Example 1, the porous carbon material composite of Example 2, and the activated carbon of Comparative Example 1 are shown in Table 3 below. Shown in Furthermore, for reference, the measurement results of redox potentials of tap water and the like are also shown in Table 3 below.

[Table 3]
PH before addition pH after addition
Example 1 7.1 9.3
Comparative Example 1 7.1 6.4
Redox potential before addition Redox potential after addition Example 1 333 mV 142 mV
Comparative Example 1 333 mV 297 mV
Redox potential tap water 547 mV
Distilled water 333mV
Commercial natural water A 321mV
Commercial natural water B 258mV

  Moreover, the graph of FIG. 1 shows the result of investigating the relationship between the addition amount of the porous carbon material of Example 1 and the activated carbon of Comparative Example 1 and pH. Furthermore, the relationship between the addition amount of the porous carbon material of Example 1 and the activated carbon of Comparative Example 1 and the oxidation-reduction potential is shown in the graph of FIG. In addition, 300 milligrams, 150 milligrams, 70 milligrams, 30 milligrams, and 10 milligrams of sample were added to 20 milliliters of distilled water, stirred for 1 minute, and the redox potential and pH of the filtered water were measured. .

  In Example 1, as compared with Comparative Example 1, the pH value of water after the addition of the porous carbon material is increased, and the redox potential value after the addition is significantly decreased. And as above-mentioned, the relative removal amount of the hydroxyl radical was 3.2, and it turned out that a hydroxyl radical can be removed with high efficiency.

  Example 2 is a modification of Example 1 and relates to a porous carbon material composite. In Example 2, a metal material (specifically, platinum fine particles, platinum nanoparticles) attached to a porous carbon material was used as the functional material. The porous carbon material was manufactured based on a method substantially similar to that described in Example 1.

More specifically, in Example 2 5 mM H ₂ PtCl ₆ aqueous solution 8 ml against distilled water 182 ml, the L- ascorbic acid (surface protective agent) was added 3.5 milligrams, Stir for a while. Thereafter, 0.43 g of the porous carbon material described in Example 1 was added, and after ultrasonic irradiation for 20 minutes, 10 ml of 40 mmol NaBH ₄ aqueous solution was added and stirred for 3 hours. Then, it filtered by suction and dried at 120 ° C. to obtain a porous carbon material composite of Example 2 as a black powder sample. Then, in the same manner as in Example 1, a cosmetic cotton that was a fiber composite for liquid application was produced.

  Even in Example 2, the liquid is applied to the fibrous member. More specifically, a liquid such as a well-known skin lotion is contained in a fibrous member, and the liquid member (skin lotion) is applied to the skin of the user's face, arms, limbs, etc. Apply and adhere. Here, the oxidative stress substance contained in the liquid (skin lotion) is removed by contacting the liquid (skin lotion) with the porous carbon material, or the liquid (skin lotion) is contacted with the porous carbon material. To lower the redox potential of the liquid (skin lotion). That is, a property such as antioxidant properties is imparted to the liquid (skin lotion).

  In Example 2, as described above, the relative removal amount of hydroxyl radicals was 7.4, and it was found that hydroxyl radicals can be removed with higher efficiency than in Example 1.

  Although the present disclosure has been described based on the preferred embodiments, the present disclosure is not limited to these embodiments, and various modifications can be made. In the examples, the case where rice husk is used as the raw material of the porous carbon material has been described, but other plants may be used as the raw material. Here, examples of other plants include pods, cocoons or stem wakame, vascular plants vegetated on land, fern plants, moss plants, algae and seaweeds, and these may be used alone. Further, a plurality of types may be mixed and used. Specifically, for example, plant-derived materials that are raw materials for porous carbon materials are rice straw (eg, from Kagoshima; Isehikari), and porous carbon materials are carbonized from raw straw as a carbonaceous material. It can be obtained by converting to (porous carbon material precursor) and then performing acid treatment. Alternatively, a plant-derived material, which is a raw material of the porous carbon material, is used as a rice bran, and a carbonaceous material (porous carbon material precursor) is obtained by carbonizing the porous carbon material as a raw material. And then acid treatment. Similar results were obtained with a porous carbon material obtained by treatment with an alkali (base) such as an aqueous sodium hydroxide solution instead of an aqueous hydrofluoric acid solution. In addition, the manufacturing method of a porous carbon material or a porous carbon material composite body can be made the same as that of Example 1 and Example 2.

  Alternatively, the plant-derived material, which is the raw material of the porous carbon material, is used as stem wakame (from Sanriku, Iwate Prefecture), and the porous carbon material is carbonized from the stem wakame as raw material to produce a carbonaceous material (porous carbon material precursor) Body) and then subjected to acid treatment. Specifically, first, for example, the stem wakame is heated at a temperature of about 500 ° C. and carbonized. In addition, you may process the stem wakame used as a raw material with alcohol before a heating, for example. As a specific treatment method, there is a method of immersing in ethyl alcohol or the like, thereby reducing moisture contained in the raw material, and other elements other than carbon contained in the porous carbon material finally obtained or , Mineral components can be eluted. Moreover, generation | occurrence | production of the gas at the time of carbonization can be suppressed by the process with this alcohol. More specifically, the stem wakame is soaked in ethyl alcohol for 48 hours. In addition, it is preferable to perform ultrasonic treatment in ethyl alcohol. Subsequently, this stem wakame is carbonized by heating in a nitrogen stream at 500 ° C. for 5 hours to obtain a carbide. In addition, by performing such a process (preliminary carbonization process), a tar component that will be generated in the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide is put in an alumina crucible and heated to 1000 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonizes at 1000 degreeC for 5 hours, and after converting into a carbonaceous substance (porous carbon material precursor), it cools to room temperature. In addition, nitrogen gas is kept flowing during carbonization and cooling. Next, the porous carbon material precursor is subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed until it becomes pH 7 using water and ethyl alcohol. And the porous carbon material can be obtained by making it dry at the end.

  Also, a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium and calcium (specifically, for example, citrus peel such as mandarin peel, orange peel, grapefruit peel, banana peel, etc. If the porous carbon material is made from the skin), a large amount of mineral components can be eluted from the porous carbon material into the water, and the hardness of the water can be controlled. In this case, the porous carbon material preferably contains 0.4 mass% or more in total of sodium (Na), magnesium (Mg), potassium (K), and calcium (Ca).

In addition, this indication can also take the following structures.
[1] << Liquid Composite for Liquid Application: First Aspect >>
A fiber composite for liquid application comprising a fibrous member containing a porous carbon material having a specific surface area value of 10 m ² / gram or more by nitrogen BET method and a pore volume of 0.2 cm ³ / gram or more by BJH method .
[2] << Liquid composite for applying liquid: second embodiment >>
The value of specific surface area by nitrogen BET method is 10 m ² / g or more, and the total volume of pores with diameters of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by delocalized density functional method is 0 A fiber composite for liquid application comprising a fibrous member containing a porous carbon material of 5 cm ³ / gram or more.
[3] << Liquid composite for liquid application: third aspect >>
In the pore size distribution determined by the delocalized density functional method having a specific surface area value of 10 m ² / gram or more by nitrogen BET method, it has at least one peak in the range of 3 nm to 20 nm, and 3 nm to 20 nm The fiber composite for liquid application which consists of the fibrous member containing the porous carbon material whose ratio of the total of the volume of the pore which has a pore diameter in the range is 0.2 or more of the total volume of all the pores.
[4] The liquid composite for fiber application according to any one of [1] to [3], wherein a functional material is attached to the porous carbon material.
[5] The fiber composite for liquid application according to any one of [1] to [4], wherein the liquid is applied to the fibrous member.
[6] The fiber composite for liquid application according to [5], in which the oxidative stress substance contained in the liquid is removed by bringing the liquid into contact with the porous carbon material.
[7] The fiber composite for liquid application according to [5], wherein the liquid is brought into contact with the porous carbon material to reduce the redox potential of the liquid.
[8] The liquid composite for fiber application according to any one of [1] to [7], wherein the raw material of the porous carbon material is a plant-derived material containing silicon.
[9] The fiber composite for liquid application according to [8], wherein the silicon content of the porous carbon material is 1% by mass or less.

Claims (9)

A fiber composite for liquid application comprising a fibrous member containing a porous carbon material having a specific surface area value of 10 m ² / gram or more by nitrogen BET method and a pore volume of 0.2 cm ³ / gram or more by BJH method . The value of specific surface area by nitrogen BET method is 10 m ² / g or more, and the total volume of pores with diameters of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by delocalized density functional method is 0 A fiber composite for liquid application comprising a fibrous member containing a porous carbon material of 5 cm ³ / gram or more. In the pore size distribution determined by the delocalized density functional method having a specific surface area value of 10 m ² / gram or more by nitrogen BET method, it has at least one peak in the range of 3 nm to 20 nm, and 3 nm to 20 nm The fiber composite for liquid application which consists of the fibrous member containing the porous carbon material whose ratio of the total of the volume of the pore which has a pore diameter in the range is 0.2 or more of the total volume of all the pores.   The fiber composite for liquid application according to any one of claims 1 to 3, wherein a functional material is attached to the porous carbon material.   The fiber composite for liquid application according to any one of claims 1 to 3, wherein the liquid is applied by including the liquid in a fibrous member.   The fiber composite for liquid application according to claim 5, wherein the oxidative stress substance contained in the liquid is removed by bringing the liquid into contact with the porous carbon material.   The fiber composite for liquid application according to claim 5, wherein the redox potential of the liquid is lowered by bringing the liquid into contact with the porous carbon material.   The fiber composite for liquid application according to any one of claims 1 to 3, wherein the raw material of the porous carbon material is a plant-derived material containing silicon.   The fiber composite for liquid application according to claim 8, wherein the content of silicon in the porous carbon material is 1% by mass or less.

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