CN102824017A - Fiber composite for application of a liquid - Google Patents
Fiber composite for application of a liquid Download PDFInfo
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- CN102824017A CN102824017A CN2012101854217A CN201210185421A CN102824017A CN 102824017 A CN102824017 A CN 102824017A CN 2012101854217 A CN2012101854217 A CN 2012101854217A CN 201210185421 A CN201210185421 A CN 201210185421A CN 102824017 A CN102824017 A CN 102824017A
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- Prior art keywords
- porous carbon
- carbon materials
- coating liquid
- liquid
- fibrous composite
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D34/00—Containers or accessories specially adapted for handling liquid toiletry or cosmetic substances, e.g. perfumes
- A45D34/04—Appliances specially adapted for applying liquid, e.g. using roller or ball
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D2200/00—Details not otherwise provided for in A45D
- A45D2200/10—Details of applicators
- A45D2200/1009—Applicators comprising a pad, tissue, sponge, or the like
- A45D2200/1018—Applicators comprising a pad, tissue, sponge, or the like comprising a pad, i.e. a cushion-like mass of soft material, with or without gripping means
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
Abstract
Provided is a fiber composite for the application of a liquid, including a fibrous member containing a porous carbon material having a specific surface area value by the nitrogen BET method of 10 m2/g or more, and a pore volume by the BJH method of 0.2 cm3/g or more.
Description
Technical field
The present invention relates to a kind of fibrous composite that is used for coating liquid.
Background technology
In recent years; From keeping the viewpoint of good health; The water of show reduction such as alkali ion water, electrolytic reduction water and hydrogen water caused concern (referring to, for example japanese unexamined patent publication number 2003-301288,2002-348208 and 2001-314877).In addition; In recent years; AMA is verified; The oxidative stress material that comprises oxygen base free radical (based on the free radical of oxygen) forms various diseases and aging reason, and said oxygen base free radical is called active oxygen such as peroxide radical, hydroxyl radical free radical, hydrogen peroxide, creating singlet oxygen by using, nitric oxide and lipid peroxide in a broad sense.It is said, the non-oxidizability cosmetics are worked on skin and remove these oxidative stress materials for preventing that various diseases is with aging very effective.
Summary of the invention
In the known scope of the inventor, still do not know to be used for liquid make-up is increased the plain mode and the means of some character such as non-oxidizability.
Therefore, expectation provides a kind of fibrous composite (fibre composites, fiber composite) that is used for coating liquid, and when the user used said composite, it provided the liquid with non-oxidizability (for example toner) easily.
First embodiment of the invention; A kind of fibrous composite that is used for coating liquid is provided; It comprises fibrous structures (cellulosic member, fibre-bearing member, fibrous member); Said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records as through nitrogen BET method
2The specific area value that/g is above, and 0.2cm as recording through the BJH method
3More than/the g, preferred 0.4cm
3The pore volume that/g is above.
Second embodiment of the invention, a kind of fibrous composite that is used for coating liquid is provided, it comprises fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records as through nitrogen BET method
2The specific area value that/g is above, and be 0.5cm through the definite total pore volume (total pore volume) of non-local density functional theory (Non Localized Density Functional Theory)
3More than/the g, preferred 1.0cm
3More than/the g, wherein said hole has 1 * 10
-9M to 5 * 10
-7Diameter in the m scope.
According to the 3rd embodiment of the present invention, a kind of fibrous composite that is used for coating liquid is provided, it comprises fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records as through nitrogen BET method
2The specific area value that/g is above, and in the pore-size distribution of confirming through the non-local density functional theory, have at least one peak in the scope at 3nm to 20nm.The ratio of cumulative volume that has the hole in the aperture (pore diameter) in 3nm to 20nm scope separately is more than 0.2 of total pore volume.
According to first to the 3rd embodiment of the present invention; The said fibrous composite that is used for coating liquid can easily provide liquid with non-oxidizability (toner (skin lotion for example; Skin lotion) etc.); Make the oxidative stress material that comprises in the said liquid (oxidative stress substances) is positively removed, and positively reduce the oxidation-reduction potential of said liquid.This specific area, pore volume and pore size distribution as recording through nitrogen BET method through the regulation porous carbon materials realizes.In addition, can use said fibrous composite through utilizing the wetting said fibrous structures of liquid (for example toner etc.).Therefore, can the liquid with the character that comprises non-oxidizability be provided through very simple mode and means.Usually, the acceptant electronics of oxidative stress material (in other words, standard oxidationreduction potential is high on positive direction).Therefore, when removing the oxidative stress material, the easy property decline that electronics is accepted (electronics give with the increase of easy property).In other words, oxidation-reduction potential becomes bigger in negative direction.
Shown in accompanying drawing, according to the detailed description of the following preferred embodiment for the present invention, of the present invention these will become more obvious with other purposes, feature and advantage.
Description of drawings
Fig. 1 shows according to the porous carbon materials of embodiment 1/according to the addition of the active carbon of comparative example 1 and the figure of the relation between the pH;
Fig. 2 shows according to the porous carbon materials of embodiment 1/according to the addition of the active carbon of comparative example 1 and the figure of the relation between the oxidation-reduction potential.
The specific embodiment
Hereinafter, will embodiment of the present invention be described with reference to accompanying drawing.The invention is not restricted to these embodiments, and the various numerical value of in the description of embodiment, mentioning and material only are exemplary.To these embodiments be described with following order.
1. the fibrous composite that is used for coating liquid of first to the 3rd embodiment according to the present invention, general description
2. embodiment 1 (fibrous composite that is used for coating liquid of first to the 3rd embodiment according to the present invention) reaches other
[fibrous composite that is used for coating liquid of first to the 3rd embodiment according to the present invention, general description]
At the fibrous composite that is used for coating liquid of first to the 3rd embodiment according to the present invention, porous carbon materials can have the form (form) that functional material is attached to it.For simplicity, can this form be called " porous carbon materials composite (porous carbon materials complex) ".
Comprising the fibrous composite that is used for coating liquid of first to the 3rd embodiment according to the present invention of above-mentioned expectation form, when utilizing the liquid infiltration fibrous structures, can be provided for the form (use form) of coating liquid.In using form, when liquid is contacted with porous carbon materials, can the oxidative stress material that be included in the liquid be removed, perhaps when liquid is contacted with porous carbon materials, can reduce the oxidation-reduction potential of liquid.In other words, the liquid that has such as the character of non-oxidizability can be provided.
The instance of liquid can be water, but is not limited thereto.For example, can mention toner, emulsion and remove cleaning products as the stain of sweat, grease, lipstick etc.
The instance of oxidative stress material can be hydroxyl radical free radical, creating singlet oxygen by using, peroxide radical, hydrogen peroxide, nitric oxide, lipid peroxide etc.Remove the oxidative stress material that comprises in the liquid and be meant that it is the state of hydrone or oxygen molecule through porous carbon materials with the reduction of oxidative stress material and with the oxidative stress substance change wherein that the state that wherein has oxidative stress material (hydroxyl radical free radical, creating singlet oxygen by using, peroxide radical, hydrogen peroxide, nitric oxide and lipid peroxide all are reactive oxygen species) is changed into.
In addition, reduced the oxidation-reduction potential of liquid.When passing through to remove dechlorination; Three halides and oxidative stress material (hydroxyl radical free radical, creating singlet oxygen by using, peroxide radical, hydrogen peroxide, nitric oxide and lipid peroxide; All be reactive oxygen species) and the state of oxidation that will wherein comprise said material is changed into and wherein (is thought on the porous carbon materials and/or the inner residual ash content that comprises mineralogical composition; Its fire and pot-life between generate) during the state of stripping, reduced the oxidation-reduction potential of liquid thus.In other words; Think because chlorine; Three halides and oxidative stress material have high positive oxidation-reduction potential (promptly; Have high acidity), so absorb, remove and highly basic/salt of weak acid (like potash) stripping helped the decline of oxidation-reduction potential through redox reaction through porous carbon materials.The oxidation-reduction potential of liquid can through use comprise the Ag/AgCl electrode as a reference the potentiometer with three electrodes of electrode measure.What expect is that the oxidation-reduction potential of reduction is below 150 millivolts.
Comprising the fibrous composite that is used for coating liquid of first to the 3rd embodiment according to the present invention of above-mentioned expectation form; Raw material in the porous carbon materials a kind of be contemplated to be contain silicon (Si) plant based material (based on the material of plant; Plant material, plant-based material).In this case; Though not concrete restriction; But a kind of in the raw material of said porous carbon materials for containing the plant based material of the above silicon of 5 quality % (Si); And said porous carbon materials comprises the silicon (Si) below the 5 quality %, expects the silicon (Si) below the 3 quality %, and more expects the silicon (Si) below the 1 quality %.
In some cases; Can apply hydrophilic treatment or hydrophobic treatments to the porous carbon materials (being referred to as " according to porous carbon materials of the present invention etc. " hereinafter) or the surface of porous carbon materials composite (porous carbon material composite, porous carbon materials complex) of the fibrous composite that is used for coating liquid (being referred to as " according to fibrous composite that is used for coating liquid of the present invention etc. " hereinafter) of first to the 3rd embodiment that formation comprises above-mentioned expectation form according to the present invention.
According to fibrous composite that is used for coating liquid of the present invention etc.; Because the small amount of carbonate that for example in carbonization and activation step, generates the fact from increasing owing to increase according to the activation grade in the porous carbon materials of the present invention etc. according to stripping the porous carbon materials of the present invention etc. and content of ashes; Make that liquid can be alkaline, perhaps can increase the pH value.In addition, on surface, generate carboxylic group (can obtain) or sulfuryl group (can obtain), thereby make that liquid can be acid, perhaps can reduce the pH value through the concentrated sulfuric acid through nitric acid treatment according to porous carbon materials of the present invention etc.Replacedly, can reducing agent such as hydrogen be added in the liquid.When liquid through according to the micro-structural of porous carbon materials of the present invention etc. the time, can change liquid structure (bunch).
According to fibrous composite that is used for coating liquid of the present invention etc., fibrous structures comprises porous carbon materials.The following concrete structure of describing according to the fibrous composite that is used for coating liquid of the present invention etc.Can be with mediating the fiber that (mixing) becomes to constitute fibrous structures according to porous carbon materials of the present invention etc., it is weaved and carries out machine crimp as required or curl so that woven cloth or nonwoven to be provided through reeling.The article of being processed by this woven cloth or nonwoven can be provided.Can use adhesive etc. to be attached to fibrous structures according to porous carbon materials of the present invention etc.Can be for example through using adhesive (adhesive agent) etc. to form the shape of expectation and be inserted between the stratiform fibrous structures according to porous carbon materials of the present invention etc.Can as required these structures be combined.Specific product by processing according to the fibrous composite that is used for coating liquid of the present invention etc. is for example cotton pads, makes up and settles material, makeup sponge for liquid foundation, cotton pads waste pad and sterilization powder puff.
The instance that constitutes the material of fibrous structures is that natural fiber is like cotton, fiber crops, bamboo, wool and slurry; TModified Cellulose Fibers; The woven cloth or the nonwoven that comprise at least a synthetic fibers, said synthetic fibers are like polypropylene, polyester, nylon, vinylon, polyethylene, polyamide, aromatic polyamides, polyolefin, polystyrene, acrylic acid, artificial silk, polyvinyl alcohol, polytetrafluoroethylene (PTFE), ethylene-vinyl alcohol base co-polymer, PETG, PTT and polybutylene terephthalate (PBT); Through fabric of knowing or the textile-like material that these material blend are obtained, yarn shape material etc.The instance of adhesive is the carboxyl nitrocellulose.Synthetic fibers can have core-sheath-type, eccentric core-sheath-type, multilayer mating type or side-by-side structure etc., and can have the cross section of circular cross section or modification.
Can be for example through as get off to make according to porous carbon materials of the present invention etc.: under 400 ℃ to 1400 ℃, plant based material is carried out carbonization, utilizes acid or alkali that said material is handled then.In the method (abbreviating " method of making porous carbon materials " hereinafter as) of manufacturing porous carbon materials according to the present invention etc., will be called " porous carbon materials precursor " or " carbonaceous material " through under 400 ℃ to 1400 ℃, plant based material being carried out the material that does not utilize acid or alkali treatment as yet that carbonization obtains.
In the method for making porous carbon materials, after acid or alkali treatment, can carry out activation processing.Perhaps, after activation processing, can carry out acid or alkali treatment.Comprise in the method for porous carbon materials of above-mentioned expectation form in manufacturing; Although depend on used plant based material; But can be before plant based material be carried out carbonization, under anaerobic state, be lower than under the temperature (for example at 400 ℃ under 700 ℃) of carburizing temperature plant based material is being heated (carbonization in advance).The result of the tar ingredients that between the carbon period, generates as the extraction meeting can reduce or remove tar ingredients.Anaerobic state can be through for example with the acquisition of getting off: the inert gas atmosphere that comprises nitrogen or argon gas is provided, vacuum atmosphere is provided, perhaps almost plant based material is carried out steaming and roasting.In the method for making porous carbon materials,, can plant based material be impregnated in the alcohol (for example methyl alcohol, ethanol and isopropyl alcohol) to reduce mineralogical composition and water content or to prevent between the carbon period, to produce stink although depend on used plant based material.In addition, in making the method for porous carbon materials, can after carry out preparatory carbonization.The plant based material that produces a large amount of pyroligneous acids (tar and light crude oil) is to be desirably in the instance that heats under the inert gas atmosphere.Marine alga as the plant based material that comprises a large amount of iodine and various mineral is that expectation utilizes alcohol to carry out pretreated instance.
In the method for making porous carbon materials, under 400 ℃ to 1400 ℃, plant based material is carried out carbonization." carbonization " among this paper is meant typically heats they are converted into carbonaceous material (for example referring to JISM0104-1984) organic substance (according to the plant based material in porous carbon materials of the present invention etc.).The instance that is used for the atmosphere of carbonization is an oxygen-free atmosphere.Particularly, the atmosphere that have vacuum atmosphere, comprises the inert gas atmosphere of nitrogen or argon gas and wherein almost plant based material is carried out steaming and roasting.Be elevated to the not restriction of programming rate of carburizing temperature, but can expecting more to expect more than 5 ℃/minute more than 3 ℃/minute for more than 1 ℃/minute under this atmosphere.The upper limit of carbonization time can be 10 hours, expects 7 hours and more expects 5 hours, but be not limited thereto.The lower limit of carbonization time can be the feasible time with plant based material carbonization positively.Can as required plant based material be ground into the granularity of expectation, perhaps with its classification.Can carry out precleaning to plant based material.In addition, the granularity that can be as required the porous carbon materials precursor or the porous carbon materials of gained be ground into expectation is perhaps with its classification.In addition, can will be ground into the granularity of expectation as required through the porous carbon materials that activation processing was handled, perhaps with its classification.In addition, can carry out sterilization to the porous carbon materials of final acquisition.The stove that is used for carbonization does not limit in shape, structure and structure aspects, and can be continuous oven or batch furnace.
In the method for making porous carbon materials composite (porous carbon materials complex), porous carbon materials is provided through acid or alkali treatment.Then, can functional material be attached to porous carbon materials.After acid or alkali treatment and before functional material is attached to porous carbon materials, can comprise the step of carrying out activation processing.The instance of functional material is the combination of platinum (Pt) or platinum (Pt) and palladium (Pd).For example, can functional material be attached to porous carbon materials with the form of fine grained or film.Particularly, can the fine grained of functional material be attached to the surface (in pore, comprising) of porous carbon materials.Perhaps, can the film of functional material be attached to the surface of porous carbon materials.Perhaps, it can be the island form, and the surface that wherein functional material is attached to porous carbon materials like " island " is like " sea ".Term " adheres to " and is meant the adhesion material different.Can functional material be attached to porous carbon materials through any following method.Can porous carbon materials be impregnated in the solution that comprises functional material so that functional material is precipitate on the surface of porous carbon materials.Can functional material be precipitate on the surface of porous carbon materials through electroless plating (chemical plating) or chemical reduction reaction.Can porous carbon materials be impregnated in the solution of the precursor that comprises functional material and heat so that functional material is precipitate on the surface of porous carbon materials.Can porous carbon materials be impregnated in the solution of the precursor that comprises functional material and be exposed to ultrasonic irradiation so that functional material is precipitate on the surface of porous carbon materials.Can porous carbon materials be impregnated in the solution of the precursor that comprises functional material to cause solgel reaction and functional material is precipitate on the surface of porous carbon materials.
As stated, in the method for making porous carbon materials, activation processing can improve the number (will be explained hereinafter) that has the micropore that is not more than the 2nm aperture separately.The instance of activation processing is gas activation and chemicals activation.In gas activation, can be with oxygen, steam, carbon dioxide, air etc. as activator.Under gas atmosphere, at 700 ℃ to 1400 ℃, expect 700 ℃ to 1000 ℃, more expect under 800 ℃ to 1000 ℃ porous carbon materials was heated dozens of minutes to several hours, thereby through volatile ingredient in the porous carbon materials and the carbon molecule micro-structural of growing.More specifically, can be as required wait and select heating-up temperature based on the kind of the type of plant based material, gas and concentration.In the chemicals activation, come porous carbon materials is carried out activation through using replacement oxygen such as zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potash, sulfate and steam, and utilize hydrochloric acid to clean.PH to porous carbon materials regulates through the use alkaline solution.Then, porous carbon materials is dry.
Can be to carrying out chemical treatment or molecule modification according to the surface of porous carbon materials of the present invention etc.For example, as chemically treated a kind of, carry out nitric acid treatment to generate carboxylic group from the teeth outwards.Through similarly handling, can on the surface of porous carbon materials, generate various functional groups such as hydroxyl, carboxyl, ketone groups or ester group with the activation processing of utilizing steam, oxygen, alkali etc.In addition, when making porous carbon materials with chemical substance that comprises hydroxyl, carboxyl, amino etc. or protein generation chemical reaction, molecule modification meeting is possible.
In the method for making porous carbon materials, from the plant based material of carbonization, remove the silicon composition through acid or alkali treatment.Said silicon composition can be the salt of Si oxide such as silica, silica and silica.Silicon composition through in the plant based material of removing carbonization can provide the porous carbon materials with high-specific surface area.In some cases, can the silicon composition in the plant based material of carbonization be removed through the dry corrosion method.In other words; In expectation form according to porous carbon materials of the present invention etc.; The plant based material that will contain silicon (Si) is as raw material, and (for example at 400 ℃ under 1400 ℃) carried out carbonization to said plant based material and be translated into porous carbon materials precursor or carbonaceous material through at high temperature.Through carbonization, the silicon in the plant based material becomes silicon composition (Si oxide) like silica (SiO
2), the salt of silica and silica, and be not carborundum (SiC).Yet even (for example at 400 ℃ under 1400 ℃) is when carrying out carbonization when at high temperature, the silicon composition (Si oxide) that before carbonization, in plant based material, comprises is also basic not to be changed.Therefore, carry out acid or alkali (or alkali) after certainly when handling, silicon composition (Si oxide) is removed like the salt of silica, silica and silica.As a result, the high-specific surface area value that records through nitrogen BET method can be provided.In addition, the expectation form according to porous carbon materials of the present invention etc. is the environment-friendly material that is derived from natural origin.Can handle the silicon composition (Si oxide) in the raw material that is included in plant based material at first through utilizing acid or alkali, and this composition removed and micro-structural is provided.Therefore, the arrangement in hole keeps the biological order property (systematicness) of plant.
As stated, a kind of of the raw material of porous carbon materials is plant based material.The limiting examples of plant based material is chaff (husk) and the bar of rice (rice), barley, wheat, rye, broomcorn millet and grain; Coffee bean, tealeaves (the for example leaf of green tea, black tea etc.); Sugarcane (bagasse especially); Corn (corn ear especially); Pericarp (for example oranges and tangerines skin such as orange peel, shaddock ped and orange peel, banana skin etc.); Reed; Undaria pinnitafida (Wakame) marine alga stem (undaria pinnitafida); The Lu Sheng vascular plant; Pteridophyte; Bryophyte; Algae; And sea grass.These materials can use separately, perhaps replacedly can make up and use multiple in these materials.The not special restriction of the shape of plant based material and form.For example, plant based material can be chaff or bar itself, perhaps its desciccate.In addition, aspect the food processing of beer, sweet wine etc., can use to comprise that fermentation, roasting fry in shallow oil or extract the various processing of (extraction).Especially, from recycling the viewpoint of trade waste, expectation be to use after handling, for example chaff after the threshing and bar.These chaffs after the processing and bar can easily obtain from for example agricultural cooperative society, alcohol manufacturing company, food company and food processing company in a large number.
Can comprise in following more than one according to porous carbon materials of the present invention etc.: magnesium (Mg), potassium (K), calcium (Ca), nonmetalloid such as phosphorus (P) and sulphur (S) and metallic element such as transition elements.For example; The amount of magnesium (Mg) can be 0.01 quality % to 3 quality %; The amount of potassium (K) can be 0.01 quality % to 3 quality %; The amount of calcium (Ca) can be 0.05 quality % to 3 quality %, and the amount of phosphorus (P) can be 0.01 quality % to 3 quality %, and the amount of sulphur (S) can be 0.01 quality % to 3 quality %.Aspect the increase of specific area value, the expectation of the amount of these elements is little.Should be understood that porous carbon materials can comprise above-mentioned other elements in addition, and can change its amount.
In the present invention, can utilize energy dispersion type x-ray spectrometer (JED-2200F that for example makes), come various elements are analyzed through energy-dispersive spectroscopy (EDS) by JEOL Ltd..Measuring condition can comprise the for example scanning voltage of 15kV and the irradiation electric current of 10 μ A.
Have many holes according to porous carbon materials of the present invention etc.Said hole comprises the aperture that has in 2nm to 50nm scope " mesopore (pore, mesopores) ", has less than " micropore " in the aperture of 2nm and has " macropore " above the aperture of 50nm.Particularly, for example, mesopore has below many 20nm of being of a size of, particularly the hole below the 10nm.For example, micropore has many holes that are of a size of about 1.9nm, about 1.5nm and about 0.8nm to 1nm.Has the 0.2cm that records through the BJH method according to expectations such as porous carbon materials of the present invention
3More than/the g, more expect 0.4cm
3More than/the g, and more expect 0.6cm
3The pore volume that/g is above.
What expect is to have the 50m that records through nitrogen BET method according to expectations such as porous carbon materials of the present invention
2More than/the g, more preferably 100m
2More than/the g, most preferably and be more preferably 400m
2The specific area value (can abbreviate " specific area value " hereinafter as) that/g is above is so that provide higher functional.
Nitrogen BET method is used for through absorbing molecules (admolecules) (being nitrogen) is adsorbed to adsorbent (in this article; Porous carbon materials)/measure adsorption isotherm from adsorbent desorption absorbing molecules, and through analyzing the data that record by the BET equality of equality (1) expression.Based on said method, can the calculated specific surface area value, pore volume etc.Particularly, when coming calculated specific surface area, at first through absorbing molecules (being nitrogen) being adsorbed to porous carbon materials/measure adsorption isotherm from porous carbon materials desorption absorbing molecules based on nitrogen BET method.Then, based on the adsorption isotherm line computation [p/{V that records of equality (1 ') cause of equality (1) or distortion
a(p
0-p)] and with it to the relative pressure (p/p in the balance
0) mapping.Regard said figure as straight line, and based on least square method come slope calculations s (=[(C-1)/(CV
m)]) and intercept i (=[1/ (CV
m)]).Based on equality (2-1) and (2-2), calculate V by the slope s and the intercept i that calculate
mAnd C.Based on equality (3), by V
mCome calculated specific surface area a
sBET (referring to BELSORP-mini and BELSORP analysis software handbook, the 62-66 page or leaf is processed by BELL Japan Inc.).Nitrogen BET method is a measuring method of " using the measuring method (Measuring methods for the specific surface area of fine ceramic powders by gas adsorption using the BET method) of BET method through the specific area of the fine ceramic powder of gas absorption " according to JIS R 1626-1996.
V
a（V
m·C·p）/[（p-p
0）{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）
Wherein,
V
a: adsorbance
V
m: the adsorbance of individual layer
P: the nitrogen pressure during balance
p
0: the saturated vapor pressure of nitrogen
L: Avogadro's number
σ: the absorption sectional area of nitrogen
When coming calculated pore volume V through nitrogen BET method
pThe time, with the adsorpting data of the adsorption isotherm that records for example linear interpolation to confirm the adsorbance V under the relative pressure of setting for calculated pore volume.Can come calculated pore volume V by adsorbance V based on equality (4)
p(referring to, BELSORP-mini and BELSORP analysis software handbook, the 62-66 page or leaf is processed by BELL Japan Inc.).Can abbreviate the pore volume of confirming through nitrogen BET method as " pore volume ".
V
p=（V/22414）×（M
g/ρ
g） （4）
Wherein,
V: the adsorbance under relative pressure
M
g: the molecular weight of nitrogen
ρ
g: the density of nitrogen
For example, can be based on the BJH method, from the pore volume rate of change with respect to the aperture, the aperture of calculating mesopore as pore size distribution.The BJH method extensively is used as and is used for the method that pore-size distribution is analyzed.When coming through the BJH method pore-size distribution analyzed, at first through absorbing molecules (being nitrogen) being adsorbed to porous carbon materials/measure adsorption isotherm from porous carbon materials desorption absorbing molecules.Then, based on the adsorption isotherm that records, when the absorbing molecules (for example nitrogen) of filler opening is confirmed the thickness of adsorption layer and the internal diameter in definite hole (twice of core radius) gradually during absorption/desorption.Based on equality (5), calculate pore radius r
pBased on equality (6), calculated pore volume.Then, through based on pore radius and pore volume, with the rate of change (dV of pore volume
p/ dr
p) to aperture (2r
p) map and acquisition pore distribution curve (referring to BELSORP-mini and BELSORP analysis software handbook, the 85-88 page or leaf is processed by BELL Japan Inc.).
r
p=t+r
k （5）
V
pn=R
n·dV
n-R
n·dt
n·c·ΣA
pj （6）
Wherein,
R
n=r
pn 2/（r
kn-1+dt
n）
2 （7）
Wherein,
r
p: pore radius
r
k: when under pressure, having pore radius r
pThe inwall in hole on the core radius (internal diameter/2) of absorption when having the adsorption layer of t thickness
V
Pn: the pore volume when the n time absorption/desorption of nitrogen
DV
n: the variable quantity when the n time absorption/desorption of nitrogen
Dt
n: the thickness t when the n time absorption/desorption of nitrogen
nVariable quantity
r
Kn: the core radius when the n time absorption/desorption of nitrogen
C: fixed value
r
Pn: the pore radius when the n time absorption/desorption of nitrogen
In addition, Σ A
PjExpression is from the integrated value of the area of the hole wall of j=1 to j=n-1.
For example, can be based on the MP method, from the pore volume rate of change with respect to the aperture, the aperture of calculating micropore as pore size distribution.When pore size distribution being analyzed, at first, nitrogen measures adsorption isotherm through being adsorbed to porous carbon materials through the MP method.Then, adsorption isotherm is converted into the pore volume (t mapping) with respect to the thickness t of adsorption layer.Based on the curvature of said figure (with respect to the thickness t of adsorption layer
nThe variable quantity of pore volume of variable quantity) obtain pore distribution curve (referring to BELSORP-mini and BELSORP analysis software handbook, 72-73, is processed by BELL Japan Inc. by 82 pages).
At JIS Z8831-2:2010 " Pore Size Distribution and Porosity of Powders; (Solid Materials)-Part 2:Method of Measuring Mesopores and Macropores using Gas Absorption; (powder; the pore-size distribution of (solid material) and porosity-Part 2: using gases adsorbs the method for measuring mesopore and macropore) " and JIS Z8831-3:2010 " Pore Size Distribution and Porosity of Powders; (Solid Materials)-Part 3:Method of Measuring Micropores using Gas Absorption "; (powder; The pore-size distribution of (solid material) and porosity-Part 3: using gases adsorbs the method for measuring micropore) the middle non-local density functional theory of stipulating; (NLDFT) method uses the program of following automatic specific area/pore size distribution measurement mechanism " BELSORP-MAX " of being made by BELL Japan Inc. as routine analyzer.As the precondition that is used to analyze, use to have columnar model and adopt carbon black (CB) to analyze.Then, will be used for pore size distribution parameter distributions function and be set at " non-supposition (no-assumption) ", and thus obtained distributed data will be carried out ten times smoothly.
Utilize acid or alkali to handle the porous carbon materials precursor.For example, can the porous carbon materials precursor be impregnated in the aqueous solution of acid or alkali.Perhaps, porous carbon materials precursor and acid or alkali are reacted in gas phase.More specifically, can use acid fluorine compounds to carry out acid treatment like hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcirm-fluoride or sodium fluoride as acid.When using fluorine compounds, the expectation of the amount of fluorine is four times of the amount of the silicon in the silicon composition that comprises in the porous carbon materials precursor, and the expectation of the aqueous solution of fluorine compounds has the above concentration of 10wt%.When through using silicon composition (for example, silica) that hydrofluoric acid comprises in the porous carbon materials precursor when removing, suc as formula (A) or (B) indicated, silica and hydrofluoric acid react, and can be used as hexafluorosilicic acid (H
2SiF
6) or ocratation (SiF
4) silicon is removed.Thus, obtained porous carbon materials.Can wash and drying material afterwards.
SiO
2+6HF→H
2SiF
6+2H
2O （A）
SiO
2+4HF→SiF
4+2H
2O （B）
When utilizing alkali (alkali) when precursor is handled, said alkali can be NaOH.When using the aqueous solution of alkali, the pH of the aqueous solution can be for more than 11.The silicon composition (for example, silica) that comprises in the porous carbon materials precursor when the aqueous solution through using NaOH is when removing, and the aqueous solution through heating NaOH makes silica suc as formula (C) indicated reacting.Can be used as the sodium metasilicate (Na that produces by reaction
2SiO
3) silicon is removed.Thus, obtained porous carbon materials.When precursor being handled, the NaOH in solid-state is heated so that it is suc as formula (C) indicated reacting through the reaction that in gas phase, causes by NaOH.Can be used as the sodium metasilicate (Na that produces by reaction
2SiO
3) silicon is removed.Thus, obtained porous carbon materials.Can wash and drying material afterwards.
SiO
2+2NaOH→Na
2SiO
3+H
2O （C）
Can be according to porous carbon materials of the present invention for comprising the porous carbon materials in hole, for example like disclosed in japanese unexamined patent publication number 2010-106007 (porous carbon materials) with so-called contrary opal structural with three-dimensional regular property.Particularly, said porous carbon materials has average pore size for 1 * 10
-9M to 1 * 10
-5The spherical hole of the three-dimensional arrangement in the m scope also has 3 * 10
2m
2The surface area that/g is above.Desirably, the similar configuration status of the crystal structure in the Kong Yiyu macroscopic perspective is arranged.Replacedly, porous carbon materials have with macroscopic perspective in the similar configuration status of (111) planar orientation of face-centred cubic structure be arranged in its lip-deep hole.
[embodiment 1]
Embodiments of the invention 1 relate to the fibrous composite that is used for coating liquid of first to the 3rd embodiment according to the present invention.
Described like first embodiment of the invention; Embodiments of the invention 1 are a kind of fibrous composites that is used for coating liquid; It comprises fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above, and 0.2cm
3More than/the g, preferred 0.4cm
3More than/the g, more preferably 0.6cm
3The pore volume that/g is above.As described second embodiment of the invention, embodiment 1 comprises a kind of fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above, and through the definite 0.5cm of non-local density functional theory
3More than/the g, preferred 1.0cm
3The total pore volume (abbreviating " volume A " as) that/g is above, wherein said hole has 1 * 10
-9M to 5 * 10
-7Diameter in the m scope.Described like the 3rd embodiment according to the present invention, embodiment 1 comprises a kind of fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above; And in the pore-size distribution of confirming through the non-local density functional theory, in 3nm to 20nm scope, has at least one peak; The ratio of volume that wherein has the hole in the aperture in 3nm to 20nm scope separately is more than 0.2 of total pore volume (corresponding to volume A), and is preferred more than 0.4.
In embodiment 1, the fibrous composite that will be used for coating liquid forms cotton pads.Fibrous structures constitutes by comprising cotton nonwoven, and has rectangular planar shape.Particularly,, fibrous structures is kneaded into fiber (cotton) in advance, spins then so that nonwoven to be provided based on known method.Thus, can obtain the fibrous composite that is used for coating liquid of embodiment 1.
In embodiment 1, utilize liquid that fibrous structures is flooded so that liquid is applied to object.More specifically, utilize the liquid of known toner that fibrous structures is flooded, and its skin with the user who comprises face, wrist and brothers is contacted said liquid (toner) is coated with or is attached to them.When making liquid (toner) when contacting, removed the oxidative stress material that in liquid (toner), comprises with porous carbon materials.In addition, when making liquid (toner) when contacting, reduced the oxidation-reduction potential of liquid (toner) with porous carbon materials.In other words, give character to liquid (toner) such as non-oxidizability.
In embodiment 1, be rice (rice) chaff as the plant based material of the raw material of porous carbon materials., utilize acid that said material is handled afterwards and obtain the porous carbon materials of embodiment 1 through thereby the chaff carbonization being translated into carbonaceous material (porous carbon materials precursor).The method of facing the manufacturing porous carbon materials of embodiment 1 down describes.
In the technology of the manufacturing porous carbon materials in embodiment 1, under the temperature in 400 ℃ to 1400 ℃ scopes plant based material (silicone content is about 20 quality %) is carried out carbonization, utilize acid or alkali that it is handled afterwards, thereby can obtain porous carbon materials.At first, under inert gas, chaff is carried out heat treated (preparation carbonization treatment).Particularly, through in nitrogen stream, under 500 ℃, heating 5 hours chaff is carried out carbonization, and obtain carbide.The feasible tar ingredients that can reduce or remove otherwise can in carburising step subsequently, produce of this processing.Afterwards, the carbide of 10g is placed in the crucible of being processed by aluminium oxide, and in nitrogen stream (10 liters/minute), the temperature of carbide is increased to 800 ℃ with 5 ℃/minute speed.Under 800 ℃, with carbide carbonization 1 hour and be translated into carbonaceous material (porous carbon materials precursor), and said material is cooled to room temperature.Keep flow of nitrogen gas in carbonization and cooling period.Then, the porous carbon materials precursor is carried out acid treatment, and water and ethanol washs to said precursor, reach 7 pH until it through spending the night in the hydrofluoric acid aqueous solution that is immersed in 46 volume %.Then, under 120 ℃, said precursor is carried out drying, and through flowing at steam in (5 liters/minute) 900 ℃ of following heating 3 hours and with its activation.Obtained the porous carbon materials (silicone content is about 0.5 quality %) of embodiment 1.
As comparative example 1, use by Wako Pure Chemical Industries the active carbon that Ltd. (with the pure medicine of light Co., Ltd.) makes.
Use measurement mechanism BELSORP-mini (by BELL JAPAN, INC. makes) to carry out the test of nitrogen absorption/desorption to obtain specific area and pore volume.Measurement balance relative pressure (p/p 0.01 to 0.99
0) under measure.Use the BELSORP routine analyzer to come calculated specific surface area and pore volume.Through using above-mentioned measurement mechanism to carry out the test of nitrogen absorption/desorption and using the BELSORP routine analyzer to calculate the pore-size distribution that obtains mesopore and micropore based on BJH method and MP method.Measure the pore size distribution of porous carbon materials through mercury injection method.Particularly, use mercury porosimeter (by the PASCAL440 of Thermo Fisher Scientific Inc. manufacturing) to carry out mercury injection method.The measurement category in hole is 10 μ m to 2nm.In addition, use by BELL JAPAN, automatic specific area/pore size distribution measurement mechanism " BELSORP-MAX " that INC. makes carries out the measurement based on non-local density functional theory (NLDFT).Before measuring, under 200 ℃, sample is carried out drying 3 hours with as preliminary treatment.
The porous material complex of the porous carbon materials of embodiment 1, embodiment 2 that the back is described and the active carbon specific area and the pore volume separately of comparative example 1 have been measured.Table 1 shows the result.In table 1, term " specific area " be meant according to nitrogen BET method obtain with m
2The specific area of/g meter.Term " MP method ", " BJH method " and " mercury injection method " are meant hole (micropore) the volume result who records through the MP method respectively, hole (mesopore is to macropore) volume result who records through the BJH method and the pore volume result who records through mercury injection method.Unit is with cm
3/ g meter.Table 2 shows the measurement result that obtains through the NLDFT method.Total pore volume is corresponding to the value of volume A.
[table 1]
| Specific area | The BJH method | The MP method | Mercury injection method | |
| Embodiment 1 | 1700 | 1.08 | 0.60 | 4.14 |
| Embodiment 2 | 1286 | 0.65 | 0.50 | |
| Comparative example 1 | 982 | 0.08 | 0.38 | 1.10 |
[table 2]
Measure following through electron spin resonance (ESR) device: the amount of removing of the hydroxyl radical free radical (OH) in the active carbon water separately of the porous material complex of the porous carbon materials of embodiment 1, embodiment 2 and comparative example 1.Particularly, the hydroxyl radical free radical that the sample of 15mg is added into 50ml produces in the solution, and stirs.Measure said solution through ESR.As a result, when with the hydroxyl radical free radical of comparative example 1 the amount of removing is regarded as 1 relatively the time, the amount of removing relatively of the hydroxyl radical free radical of embodiment 1 is 3.2, and the amount of removing relatively of the hydroxyl radical free radical of the embodiment 2 that describes of back is 7.4.
Measured the pH and the oxidation-reduction potential of active carbon water separately of porous material complex and the comparative example 1 of the porous carbon materials of embodiment 1, embodiment 2 that the back is described.Table 3 shows the result.For reference, table 3 also shows the result of the oxidation-reduction potential of running water etc.
[table 3]
Fig. 1 shows according to the porous carbon materials of embodiment 1/according to the addition of the active carbon of comparative example 1 and the figure of the relation between the pH.Fig. 2 shows according to the porous carbon materials of embodiment 1/according to the addition of the active carbon of comparative example 1 and the figure of the relation between the oxidation-reduction potential.Measure the oxidation-reduction potential and the pH of water through the sample that in the distilled water of 20ml, adds 300mg, 150mg, 70mg, 30mg or 10mg.With each sample solution stirring 1 minute, filter then.
In embodiment 1, compare with comparative example 1, the pH of the water behind the interpolation porous carbon materials raises, and the oxidation-reduction potential after adding significantly reduces.As stated, the amount of removing relatively of hydroxyl radical free radical is 3.2.Disclosed, can remove hydroxyl radical free radical with high efficiency.
[embodiment 2]
Embodiment 2 is replacement schemes of embodiment 1 and relates to porous carbon materials complex (porous carbon material composite, porous carbon materials composite).In embodiment 2,, used the metal_based material (based on the material of metal, the metal species material) (platinum micro mist, nano platinum particle particularly) that is attached to porous carbon materials as functional material.Similar approach through described in the embodiment 1 is made porous carbon materials.
Particularly, in embodiment 2, with the 5mmol H of 8ml
2PtC
16The L-ascorbic acid (surface protectant) of solution and 3.5mg adds in the distilled water of 182ml, and stirs a moment.Afterwards,, utilize ultrasonic wave to its irradiation 20 minutes to wherein being added on the 0.43g porous carbon materials described in the embodiment 1, and to the 40mmol NaBH that wherein adds 10ml
4Solution stirred 3 hours then.Then, carry out drying under suction filtration and 120 ℃ so that the black powder sample to be provided, that is, and the porous carbon materials complex of embodiment 2.Through making the cotton pads of processing by the fibrous composite that is used for coating liquid with the similar method of method described in the embodiment 1.
In addition, in embodiment 2, utilize liquid that fibrous structures is flooded so that liquid is applied to object.More specifically, utilize the liquid of known toner that fibrous structures is flooded, and its skin with the user who comprises face, wrist and brothers is contacted said liquid (toner) is coated with or is attached to them.When making liquid (toner) when contacting, removed the oxidative stress material that in liquid (toner), comprises with porous carbon materials.In addition, when making liquid (toner) when contacting, reduced the oxidation-reduction potential of liquid (toner) with porous carbon materials.In other words, give character to liquid (toner) such as non-oxidizability.
In embodiment 2, as stated, the amount of removing relatively of hydroxyl radical free radical is 7.4.Disclosed, can be to remove hydroxyl radical free radical than efficient higher among the embodiment 1.
It is illustrated, and the invention is not restricted to said embodiment and can make amendment in every way based on embodiment of the present invention.When in an embodiment chaff being used as the raw material of the porous carbon materials of being processed by rice bran, can use other plant.For example, other available plants comprise bar, reed, the stem of undaria pinnitafida marine alga, Lu Sheng vascular plant, pteridophyte, bryophyte, algae and sea grass.These materials can use separately, and replacedly can make up and use multiple in these plants.Particularly, rice chaff (for example, Isehikari is made by the Kagoshima (Kagoshima prefecture) of Japan) can be the plant based material as the raw material of porous carbon materials.Can the chaff carbonization be become carbonaceous material (porous carbon materials precursor), and can utilize acid that carbonaceous material is handled to obtain porous carbon materials.Replacedly, rice section reed can be the plant based material as the raw material of porous carbon materials.Can the reed carbonization of rice section be become carbonaceous material (porous carbon materials precursor), and can utilize acid that carbonaceous material is handled to obtain porous carbon materials.Realize and above-mentioned confers similar advantages through replacing the aqueous solution of hydrofluoric acid that material is handled the porous carbon materials that obtains via the aqueous solution that uses alkali (alkali) like NaOH.Make porous carbon materials or porous carbon materials complex method can with embodiment 1 and 2 in similar.
Replacedly, the stem of undaria pinnitafida marine alga (Japanese rock hand county, (cropped in Sanriku, Iwate prefecture in Japan) produced in three lands) can be the plant based material as the raw material of porous carbon materials.Can the stem carbonization of undaria pinnitafida marine alga be become carbonaceous material (porous carbon materials precursor), and can utilize acid that carbonaceous material is handled to obtain porous carbon materials.Particularly, under 500 ℃ temperature for example, the stem of undaria pinnitafida marine alga heated and with its carbonization.Before heating, can utilize alcohol that the stem of undaria pinnitafida marine alga is handled.Particularly, can utilize ethanol etc. that raw material is flooded.As a result, the moisture that comprises in the raw material reduces, and said processing also make can stripping carbon and mineralogical composition element in addition, it otherwise is included in the porous carbon materials of final acquisition.The processing of utilization alcohol has suppressed the generation of the gas during the carbonization treatment.More specifically, the stem with the undaria pinnitafida marine alga flooded in ethanol 48 hours.Be desirably in the ethanol said material is carried out sonicated.Then, thus through in nitrogen stream 500 ℃ down heating came stems to the undaria pinnitafida marine alga to carry out carbonization in 5 hours to obtain carbide.This processing (preparation carbonization treatment) can reduce or remove the tar ingredients that otherwise in carburising step subsequently, produces.Afterwards, the carbide of 10g is placed in the crucible of being processed by aluminium oxide, and in nitrogen stream (10 liters/minute), the temperature of carbide is increased to 1000 ℃ with 5 ℃/minute speed.Under 1000 ℃, to carbide carbonization 5 hours and be translated into carbonaceous material (porous carbon materials precursor), and said material is cooled to room temperature.Keep flow of nitrogen gas in carbonization and cooling period.Then, the porous carbon materials precursor is carried out acid treatment, and water and ethanol washs to said precursor, reach 7 pH until it through spending the night in the hydrofluoric acid aqueous solution that is immersed in 46 volume %.At last, said precursor is carried out drying, thereby obtain porous carbon materials.
When comprising at least a plant that is selected from the group of forming by sodium, magnesium, potassium and calcium (particularly; For example oranges and tangerines skin such as orange peel; Orange peel and shaddock ped and banana skin) when being used as the raw material of porous carbon materials; Porous carbon materials makes can be with a large amount of mineralogical composition strippings to water, and even can control hardness of water.In this case, expectation be, the sodium that comprises (Na), magnesium (Mg), the total amount of potassium (K) or calcium (Ca) is more than the 0.4 quality %.
The present invention can have following structure.
[1] " fibrous composite that is used for coating liquid: first embodiment "
A kind of fibrous composite that is used for coating liquid, it comprises fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records as through nitrogen BET method
2The specific area value that/g is above, and 0.2cm as recording through the BJH method
3More than/the g, preferred 0.4cm
3The pore volume that/g is above.
[2] " fibrous composite that is used for coating liquid: second embodiment "
A kind of fibrous composite that is used for coating liquid comprises fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above, and through the definite 0.5cm of non-local density functional theory
3More than/the g, preferred 1.0cm
3The total pore volume that/g is above, wherein said hole has 1 * 10
-9M to 5 * 10
-7Diameter in the m scope.
[3] " fibrous composite that is used for coating liquid: the 3rd embodiment "
A kind of fibrous composite that is used for coating liquid comprises fibrous structures, and said fibrous structures contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above, and through at least one peak in the definite pore-size distribution in the scope of 3nm to 20nm of non-local density functional theory, and the ratio of the cumulative volume in the hole of diameter in 3nm to 20nm scope is more than 0.2 of total pore volume.
[4] according to each the fibrous composite that is used for coating liquid in above-mentioned [1] to [3], wherein,
Functional material is attached to said porous carbon materials.
[5] according to each the fibrous composite that is used for coating liquid in above-mentioned [1] to [4], wherein,
Said fibrous structures is configured to be impregnated with liquid, makes to be coated with said liquid.
[6] according to the fibrous composite that is used for coating liquid of above-mentioned [5], wherein,
Said porous carbon materials is configured to contact with said liquid, thereby the oxidative stress material that comprises in the said liquid is removed.
[7] according to the fibrous composite that is used for coating liquid of above-mentioned [5], wherein,
Liquid is contacted with said porous carbon materials, make the oxidation-reduction potential of said liquid descend.
[8] according to each the fibrous composite that is used for coating liquid in above-mentioned [1] to [7], wherein,
The a kind of of raw material in the said porous carbon materials is the plant based material that contains silicon.
[9] according to the fibrous composite that is used for coating liquid of above-mentioned [8], wherein,
Said silicone content is below the 1 quality %.
Embodiment of the present invention and embodiment are described, but the invention is not restricted to the foregoing in said embodiment and embodiment, described, and in technical scope of the present invention, various modifications are possible.
For example, above-mentioned numerical value, structure, structure, shape and the material among embodiment and the embodiment only is instance, and can use as required and its different numerical, structure, structure, shape, material etc.
The present invention comprise with on the June 13rd, 2011 of relevant theme of disclosed content in the japanese priority patent application JP 2011-130967 that Japan Patent office submits to, through reference its full content is incorporated herein.
It should be understood by one skilled in the art that according to designing requirement and other factors, can carry out various changes, combination, son combination and change, as long as they are in the scope of accompanying claims or its equivalent.
Claims (11)
1. a fibrous composite that is used for coating liquid comprises the fibrous structures that contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above, and the 0.2cm that records through the BJH method
3The pore volume that/g is above.
2. a fibrous composite that is used for coating liquid comprises the fibrous structures that contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above, and through the definite 0.5cm of non-local density functional theory
3The total pore volume that/g is above, wherein said hole has 1 * 10
-9M to 5 * 10
-7Diameter in the m scope.
3. a fibrous composite that is used for coating liquid comprises the fibrous structures that contains porous carbon materials, and said porous carbon materials has the 10m that records through nitrogen BET method
2The specific area value that/g is above; Passing through in the definite pore-size distribution of non-local density functional theory of said porous carbon materials; In the scope of 3nm to 20nm, have at least one peak, and the shared ratio of the cumulative volume in the hole of aperture in 3nm to 20nm scope is more than 0.2 of total pore volume.
4. according to each described fibrous composite that is used for coating liquid in the claim 1 to 3, wherein,
Functional material is attached to said porous carbon materials.
5. according to each described fibrous composite that is used for coating liquid in the claim 1 to 3, wherein,
Said fibrous structures is configured to be impregnated with liquid, makes to be coated with said liquid.
6. the fibrous composite that is used for coating liquid according to claim 5, wherein,
Said porous carbon materials is configured to contact with said liquid, makes to remove the oxidative stress material that comprises in the said liquid.
7. the fibrous composite that is used for coating liquid according to claim 5, wherein,
Said porous material is configured to contact with said liquid, makes the oxidation-reduction potential of said liquid reduce.
8. according to each described fibrous composite that is used for coating liquid in the claim 1 to 3, wherein,
The a kind of of raw material in the said porous carbon materials is the plant based material that contains silicon.
9. the fibrous composite that is used for coating liquid according to claim 8, wherein,
The silicone content of said porous carbon materials is below the 1 quality %.
10. according to each described fibrous composite that is used for coating liquid in the claim 1 to 3, wherein, hydrophilic treatment or hydrophobic treatments are implemented in the surface of said porous carbon materials.
11. according to each described fibrous composite that is used for coating liquid in the claim 1 to 3, wherein, said porous carbon materials comprises more than one in magnesium (Mg), potassium (K), calcium (Ca), nonmetalloid and the transition elements.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011130967A JP5810652B2 (en) | 2011-06-13 | 2011-06-13 | Fiber composite for liquid application |
| JP2011-130967 | 2011-06-13 |
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| Publication Number | Publication Date |
|---|---|
| CN102824017A true CN102824017A (en) | 2012-12-19 |
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|---|---|---|---|
| CN2012101854217A Pending CN102824017A (en) | 2011-06-13 | 2012-06-06 | Fiber composite for application of a liquid |
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|---|---|
| US (2) | US20120315477A1 (en) |
| JP (1) | JP5810652B2 (en) |
| CN (1) | CN102824017A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103972521A (en) * | 2013-02-05 | 2014-08-06 | 索尼公司 | Electrode material, electrode, and battery |
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| JP2013035251A (en) * | 2011-08-10 | 2013-02-21 | Sony Corp | Three-dimensional shaped article, method of manufacturing the same, and liquid composition for manufacturing three-dimensional shaped article |
| US10517879B2 (en) * | 2015-12-17 | 2019-12-31 | Performance Labs PTE. LTD. | Device and method of using volatile organic compounds that affect mood, emotion or a physiologic state |
| BR112020021595A2 (en) * | 2018-07-31 | 2021-02-17 | Toray Industries, Inc. | carrier to adsorb organic matter, and column for adsorption. |
| CN113913969B (en) * | 2021-11-18 | 2023-03-17 | 因达孚先进材料(苏州)有限公司 | Method for preparing hydrophobic activated carbon fiber from carbon felt leftover material |
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| CN101541676A (en) * | 2007-04-04 | 2009-09-23 | 索尼株式会社 | Porous carbon material, process for producing the same, adsorbent, mask, adsorbent sheet and supporting member |
| CN101573470A (en) * | 2006-12-29 | 2009-11-04 | 3M创新有限公司 | Plasma deposited microporous carbon material |
| JP2009299211A (en) * | 2008-06-11 | 2009-12-24 | Omikenshi Co Ltd | Moisture-retaining rayon fiber and moisture-retaining nonwoven fabric sheet |
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| JP2001146626A (en) * | 1999-11-17 | 2001-05-29 | Lion Corp | Carbon particle-containing fiber and fiber product using the fiber |
| JP2003153738A (en) * | 2001-11-19 | 2003-05-27 | Takashi Kosako | Cleansing cotton for astringent lotion |
| JP2008174864A (en) * | 2007-01-18 | 2008-07-31 | Kenji Nakamura | Make-up cotton |
-
2011
- 2011-06-13 JP JP2011130967A patent/JP5810652B2/en active Active
-
2012
- 2012-06-06 US US13/489,864 patent/US20120315477A1/en not_active Abandoned
- 2012-06-06 CN CN2012101854217A patent/CN102824017A/en active Pending
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2015
- 2015-05-08 US US14/707,494 patent/US20150237988A1/en not_active Abandoned
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| CN101573470A (en) * | 2006-12-29 | 2009-11-04 | 3M创新有限公司 | Plasma deposited microporous carbon material |
| CN101541676A (en) * | 2007-04-04 | 2009-09-23 | 索尼株式会社 | Porous carbon material, process for producing the same, adsorbent, mask, adsorbent sheet and supporting member |
| JP2009299211A (en) * | 2008-06-11 | 2009-12-24 | Omikenshi Co Ltd | Moisture-retaining rayon fiber and moisture-retaining nonwoven fabric sheet |
| CN101888970A (en) * | 2008-09-29 | 2010-11-17 | 索尼公司 | Porous carbon material composite, method for producing same, adsorbent, cosmetic preparation, purifying agent and photocatalyst composite material |
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| CN103972521A (en) * | 2013-02-05 | 2014-08-06 | 索尼公司 | Electrode material, electrode, and battery |
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| Publication number | Publication date |
|---|---|
| JP2013000156A (en) | 2013-01-07 |
| JP5810652B2 (en) | 2015-11-11 |
| US20120315477A1 (en) | 2012-12-13 |
| US20150237988A1 (en) | 2015-08-27 |
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Application publication date: 20121219 |