MEDICAL MASK WITH A FUNCTIONAL MATERIAL
The purpose of the invention is to provide a surgical mask with sufficient antibacterial properties, by uniformly manifesting on the surface of nanofibers a functional material with antibacterial and antiviral properties. The problem is solved by a mask with a functional material which comprises a nanofiber containing at least one base polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinyl chloride, polyurethane, polyester, zein, collagen and methoxymethylated nylon, and at least one functional substance selected from a group consisting of catechin polyphenols, persimmon tannin polyphenols, grape seed polyphenols, soybean polyphenols, lemon peel polyphenols, coffee polyphenols, phenylcarboxylic acid, ellagic acid and coumalin, and having a diameter of 1 nm to 2000 nm.
The invention relates to a medical mask with a functional material.
BACKGROUND ARTTechniques for manufacturing a nanometer sized polymer fiber by an electrospinning method have been known (Patent Literature 1). In the techniques, a polymer solution is released from a nozzle installed on the tip of a container in which the polymer solution as a raw material accumulates to a target electrode to which a high voltage is applied, thereby the polymer solution transfers from the nozzle to the target electrode, during that time, it becomes fibrous fibers along the line of electric force to manufacture the polymer fibers on the target electrode. This method allows manufacture of ten to several hundreds nanometer-ordered fibers or a sheet or a mat composed by gathering the fibers (nano fiver assembly).
A polymeric nanofiber manufactured by the electrospinning method has a smooth surface, and it is not necessarily easy to add surficial decorations and functions. For this reason, when a substance other than a polymer is mixed in a polymer, the substance is embedded in the polymer of the nanofiber, and it may not exert the original functions.
Meanwhile, technologies to provide a mask for protecting pollen (Patent Literature 1), a water-soluble sheet (Patent Literature 3), a nanofiber containing a functional material (Patent Literature 4) or the like from fibers manufactured by electrospinning methods have been developed.
CITATION LIST Patent Literature
- Patent Literature 1: U.S. Pat. No. 6,656,394
- Patent Literature 2: Japanese Published Unexamined Patent Application No. 2010-274102
- Patent Literature 3: Domestic Re-Publication of PCT International Publication No. 2009/031620
- Patent Literature 4: Japanese Published Unexamined Patent Application No. 2008-38271
However, in prior art (e.g. Patent Literature 4), the functional material cannot be said to be sufficiently and uniformly dispersed or dissolved in the nanofiber, and it is non-uniformly contained, thus it could not sufficiently exert the effects of the functional material.
The invention was made in light of the above-mentioned circumstances, and the object is, for example, to provide a functional material-based mask having sufficient antimicrobial properties by evenly expressing a functional material having antimicrobial properties and antiviral properties on a surface of a nanofiber.
Means for Solving the ProblemsThe inventors made the invention after many keen examinations. The invention for solving the problems are followings.
[1] A mask with a functional material which comprises a nanofiber containing at least one base polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinyl chloride, polyurethane, polyester, zein, collagen and methoxymethylated nylon, and at least one functional substance selected from a group consisting of catechin polyphenols, persimmon tannin polyphenols, grape seed polyphenols, soybean polyphenols, lemon peel polyphenols, coffee polyphenols, phenylcarboxylic acid, ellagic acid and coumalin, and having a diameter of 1 nm to 2000 nm.
[2] A mask with a functional material which comprises not only the nanofiber described in [1] but also a reinforcing nanofiber containing at least one reinforcing polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinyl chloride, polyester, zein, collagen and polyurethane and having a diameter of 1 nm to 2000 nm.
[3] The mask with the functional material according to [1] or [2], wherein the functional substance is uniformly dispersed or dissolved in the base polymer.
[4] The mask with the functional material according to any one of [1] to [3] which consists of only the base polymer and the functional substance.
[5] The mask with the functional material according to any one of [1] to [4], wherein a weight per unit area of the nanofiber is 0.005 g/m2 to 10 g/m2.
[6] The mask with the functional material according to any one of [1] to [5], wherein an air-permeability is 1 cc/cm2·sec to 1000 cc/cm2·sec.
[7] The mask with the functional material according to any one of [1] to [6], wherein a resin constituting the resin composition mask is negatively or positively electrostatically-charged and attracts surrounding substances positively or negatively electrostatically-charged.
[8] The mask with the functional material according to any one of [1] to [7] which is a surgical mask, wherein the resin composition mask is composed of a non-woven fabric and is for surgical applications.
[9] The surgical mask according to [8], wherein a trapping performance for fine particles of 0.1 μm or larger is 99% or more.
[10] The surgical mask according to [8], wherein a trapping performance for fine particles of 3 μm or larger is 99% or more.
[11]A manufacturing method for the mask according to any one of [1] to [10], wherein a polymer-containing solution is prepared by dissolving at least one base polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinylidene chloride, polyester, zein, collagen, polyvinyl chloride, methoxymethylated nylon and polyurethane in at least one solvent selected from a solvent group consisting of water, acetone, methanol, ethanol, propanol, toluene, benzene, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylsulfoxide, 1,4-dioxane, carbon tetrachloride, methylene chloride, pyridine, N-methyl-2-pyrrolidone, ethylene carbonate, diethyl carbonate, propylene carbonate, acetonitrile, lactic acid, acetic acid, dimethylacetamide, dimethylformamide, dichloromethane, trichloromethane, hexafluoroisopropanol, formic acid, chloroform, formaldehyde and acetaldehyde; a functional substance-containing solution is prepared by dissolving at least one functional substance selected from a group consisting of catechin polyphenols, persimmon tannin polyphenols, grape seed polyphenols, soybean polyphenols, lemon peel polyphenols, coffee polyphenols, phenylcarboxylic acid, ellagic acid and coumalin in at least one solvent selected from the solvent group; a mixed solution is prepared by mixing the polymer-containing solution and the functional substance-containing solution; and the mask is manufactured from a fiber made by spinning this mixed solution by an electrospinning method.
[12] The manufacturing method for the mask according to [11], wherein any of the solvents for preparing the polymer-containing solution and the functional substance-containing solution is any one selected from a group consisting of formic acid, hexafluoroisopropanol, water, dimethylformamide, ethanol and dichloromethane.
[13] The manufacturing method for the mask according to [11] or [12], wherein the functional substance-containing solution contains sodium chloride.
[14] The manufacturing method for the mask according to any one of [11] to [13], wherein the mixed solution is uniform in properties and transparent.
In manufacturing the mask, a method in which when the nanofiber non-woven fabric is spun, a non-woven fabric with a diameter of 1 nm to 10 cm is used as a collector to spin it on the non-woven fabric, or a method in which only the nanofiber non-woven fabric is spun, then it is adhered to the non-woven fabric with a diameter of 1 nm to 10 cm by thermocompression bonding or an adhesive component such as a solvent, can be adopted.
Advantageous Effects of the InventionAccording to the present invention, a non-woven fabric containing functional substances uniformly on the nanofiber can be provided. Since this nanofiber non-woven fabric has both functions of the nanofiber and functions of catechins as the functional substances, it has antioxidative effects, antimicrobial effects, antiviral effects, deodorizing effects, harmful substance-adsorbing effects, antifungal effects and the like. Thus, it can be preferably used for a mask with functional material, particularly for a surgical mask.
Next, a detailed explanation of the embodiment of the present invention will be given. The technical scope of the present invention is not limited to the following embodiments but can be performed by various modifications without changing the gist of the invention. In addition, the technical scope of the present invention reaches the equivalent range.
The PVA used in the present invention means a kind of synthetic resin represented by a rational formula (—CH2CH(OH)—)n, and has very high hydrophilicity due to the inclusion of many hydroxyl groups and is soluble in hot water.
The polylactic acid means a kind of biodegradable plastic which was produced as high-molecular-weight products by chaining a plurality of lactic acids (CH3CH(OH)COOH) as a unit. The lactic acid as a material for manufacturing the polylactic acid can be produced from vegetables (e.g. corn, cassava, sugar cane, beet, sweet potato, etc.). For manufacturing the polylactic acid, generally, a lactic acid is cyclized to produce a lactide, and this is turned into the polylactic acid by ring-opening polymerization, but the manufacturing method of the polylactic acid is not particularly limited in the present invention.
It is known that the lactic acid as an elementary substance constituting the polylactic acid includes two types, L- and D-optical isomers. The present invention can also be used for polylactic acids manufactured using any of L- and D-lactic acids as a unit (alternatively, for polylactic acids comprising L- and D-lactic acids at any ratio).
The fibroin means a kind of fibrous protein which is a principal component of silken threads.
The chitosan mainly means β-1,4-polyglucosamine, which is a deacetylation of chitin. Although the chitosan is mainly composed of a β-1,4-polyglucosamine structure, its structure may be somewhat changed because it is manufactured by dissolving the chitin with a concentrated alkali.
The chitin means a linear nitrogen-containing polysaccharide polymer comprising a poly-β1-4-N-acetylglucosamine. It is known as a principal component of the exoskeleton of arthropods and crustaceans.
Nylon 6, Nylon 66, Nylon 9T and Nylon 610 mean kinds of polyamide synthetic fibers.
The polyamide means a polymer composed by bonding a large number of monomers through amide bonds.
The polystyrene means a polymer composed by bonding a large number of styrenes.
The polyacrylonitrile means a kind of organic polymer obtained by polymerizing acrylonitriles.
The polyethylene terephthalate means a kind of polyester formed by dehydrocondensation of ethyleneglycol and terephthalic acid.
The polyvinyl chloride means a kind of polymeric compound obtained by polymerization of vinyl chloride or by copolymerization with vinyl acetate or the like.
The polyvinylidene chloride means a synthetic resin composed by polymerizing vinylidene groups including chlorine.
The polyester means a polycondensate of a polyvalent carboxylic acid and a polyalcohol.
The zein is a main protein of a corn seed and belongs to prolamins. The prolamin belongs to simple proteins, can be dissolved in a 60% to 90% ethanol and is the general term for proteins insoluble in an over 90% ethanol, water and a neutral salt solution, and other examples include gliadin of wheat, hordein of barley and the like. The zein is composed of various molecular species, and main components have molecular weights of 22000 and 19000.
The collagen means the main protein component constituting connective tissues in animals. In mammals, it accounts for approximately 30% of the total proteins in a body. The collagen comprises 10 or more kinds of protein superfamilies like type I and II collagens, and contains a large amount of glycine and proline. In the present invention, any type of collagen or mixture can be used.
The catechin polyphenols mean water-soluble polyhydric phenols which are abundantly contained in plants such as tea. In a classification method for the catechins, they are classified into unpolymerized catechins and polymerized catechins. In addition, the unpolymerized catechins include gallate types including a catechin gallate, epicatechin gallate, gallocatechin gallate and epigallocatechin gallate, and non-gallate types including catechin, epicatechin, gallocatechin and epigallocatechin. In further classification method, the catechins are classified into epi types including epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate, and non-epi types including catechin, gallocatechin, catechin gallate and gallocatechin gallate.
The catechin oligomer means an oligomer composed of a plurality of, 3 to 10 catechins bound to each other. Although the catechins include a plurality of types as mentioned above, any catechin oligomer to which any molecules of them (including homogeneity or heterogeneity) are bound can be used in the present invention.
The persimmon tannin polyphenols mean polyphenols derived from juice obtained from fruits of astringent persimmons. The persimmon tannin polyphenols contain tannin, catechin, flavonoid and the like.
The grape seed polyphenols mean polyphenols derived from juice obtained from grape seeds. The grape seed polyphenols contain anthocyanin and the like.
The soybean polyphenols mean polyphenols derived from sap obtained from soybeans. The soybean polyphenols contain isoflavone, anthocyanin and the like.
The lemon peel polyphenols mean polyphenols derived from juice obtained from lemon peel. The lemon peel polyphenols contain hesperidin and the like.
The coffee polyphenols mean polyphenols obtained from sap of coffee beans. The coffee polyphenols contain bitterness components like a chlorogenic acid.
It should be noted that “the catechin polyphenols, persimmon tannin polyphenols, grape seed polyphenols, soybean polyphenols, lemon peel polyphenols, coffee polyphenols, phenylcarboxylic acid, eliagic acid and coumalin” are collectively called “polyphenol compounds” in the specification. In addition, the polyphenol compounds are included in the functional substances of the invention of the present application.
The nanofiber of the present invention means a fiber having a single yarn diameter of about 1 nm to about 2000 nm, and when it is manufactured by the electrospinning method, a non-woven fabric is composed of the nanofiber assembly. The nanofiber obtained as a non-woven fabric is effectively used as a mask, particularly as a surgical mask.
Extremely low air-permeability of the mask is unfavorable because of labored breathing. In addition, although a mask having high air-permeability is favorable, it may lead to significant technical problems. For this reason, an upper limit value of the air-permeability is, but not particularly limited to, 1000 cc/cm2·sec or less, preferably 500 cc/cm2·sec or less, more preferably 300 cc/cm2·sec or less, and a lower limit value is 1 cc/cm2·sec or more, preferably 100 cc/cm2·sec or more, more preferably 150 cc/cm2·sec or more.
For manufacturing the non-woven fabric, a base polymer is dissolved in a proper solvent (inorganic solvent such as water, acid amide-based solvent (including protic polar solvent, aprotic polar solvent), organic acid solvent (particularly including a solvent containing carboxylic acid or sulfonic acid)). Aside from this, a polyphenol compound is dissolved in an organic acid solvent (particularly including a solvent containing the carboxylic acid or sulfonic acid).
For preparing a biodegradable polyester-containing solution (or a polymer-containing solution), 1 part by mass to 50 parts by mass (preferably 3 parts by mass to 20 parts by mass, more preferably 3 parts by mass to 10 parts by mass) of base polymer is dissolved in 50 parts by mass to 99 parts by mass (preferably 80 parts by mass to 97 parts by mass, more preferably 90 parts by mass to 99 parts by mass) of solvent. In addition, for preparing a functional substance-containing solution, 0.001 parts by mass to 70 parts by mass (preferably 0.1 parts by mass to 60 parts by mass, more preferably 1 part by mass to 50 parts by mass) of functional substance is dissolved in 30 parts by mass to 99.999 parts by mass (preferably 40 parts by mass to 99.999 parts by mass, more preferably 50 parts by mass to 99.999 parts by mass). Additionally, the biodegradable polyester-containing solution (or the polymer-containing solution) and the functional substance-containing solution are mixed in a ratio of 50 parts by mass to 99.999 parts by mass: 0.0001 parts by mass to 50 parts by mass (preferably 60 parts by mass to 99.999 parts by mass: 0.0001 parts by mass to 40 parts by mass, more preferably 75 parts by mass to 99 parts by mass: 1 part by mass to 25 parts by mass). In the nanofiber manufactured in this way, the ratio of the polymer to the functional substance is 50 parts by mass to 99.9999 parts by mass: 50 parts by mass to 0.0001 parts by mass (preferably 60 parts by mass to 99.9999 parts by mass: 40 parts by mass to 0.0001 parts by mass).
Subsequently, both solutions are mixed to prepare a mixed solution. In the present invention, since the mixed solution is transparent, the polyphenol compound is also in a dissolved state (not in a suspended state). Thus, also when the electrospinning method is carried out, the polyphenol compound is uniformly allocated in the nanofiber.
The functional substance-containing solution can comprise sodium chloride (NaCl). This is preferable because a fiber with an ultrasmall diameter can be stably made. Also, a concentration of sodium chloride is preferably 0.001 mass % to 1 mass, more preferably 0.01 mass % to 0.1 mass %.
The electrospinning method is carried out using the mixed solution. The electrospinning method may be affected by factors such as a concentration of a spinning base material, a type of solvent, a diameter of a needle, an injection range, a rotating speed, a voltage and an injection speed. The nanofiber non-woven fabric can actually be manufactured by properly combining the factors.
As a test for evaluating trapping performances of fine particles with a size of 0.1 μm or larger, an evaluation by PFE (Particulate Filtration Efficiency) can be made.
Also, as a test for evaluating trapping performances of fine particles with a size of 3 μm or larger, an evaluation by BFE (Bacterial Filtration Efficiency) can be made.
EXAMPLESNext, the present invention will be detailed with reference to Examples and Tests, but the present invention is not limited to these Examples and Tests.
Example 1 Polylactic Acid+Catechin Polyphenol+NaClA polylactic acid (Mitsui Chemicals, Inc.) was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of polylactic acid and 90 g of dichloromethane were mixed and a polylactic acid resin was dissolved at normal temperature (about 25° C.) to prepare a biodegradable polyester-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution), in which 0.01 wt % of NaCl was further dissolved. The two solutions, 7.5 g of biodegradable polyester-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a colorless and transparent mixed solution. This mixed solution (transparent solution containing the polylactic acid and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that a distance from a inner bore on the syringe needle tip to a fibrous material-collecting electrode was set to 10 cm to 200 cm, to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polylactic acid (Mitsui Chemicals, Inc.) was used as a base polymer, and a catechin polyphenol (Sunphenon EGCg, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon EGCg)”) was used as a functional substance to make a non-woven fabric.
10 g of polylactic acid and 90 g of dichloromethane were mixed and a polylactic acid resin was dissolved at normal temperature (about 25° C.) to prepare a biodegradable polyester-containing solution (polymer-containing solution). In addition, dimethylformamide was added to the catechin (Sunphenon EGCg) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of biodegradable polyester-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a transparent mixed solution. This mixed solution (transparent solution containing the polylactic acid and catechin EGCg) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm, to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polylactic acid (Mitsui Chemicals, Inc.) was used as a base polymer, and a persimmon tannin polyphenol (odorless persimmon tannin: Osugi Co., ltd.) was used as a functional substance to make a non-woven fabric.
10 g of polylactic acid and 90 g of dichloromethane were mixed and a polylactic acid resin was dissolved at normal temperature (about 25° C.) to prepare a biodegradable polyester-containing solution (polymer-containing solution). In addition, dimethylformamide was added to the persimmon tannin polyphenol and dissolved to prepare a solution containing 20 wt % of polyphenol compound (functional substance-containing solution). Of the two solutions, 7.5 g of biodegradable polyester-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a transparent mixed solution. This mixed solution (transparent solution containing the polylactic acid and persimmon tannin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyvinyl alcohol (Wako Pure Chemical Industries, Ltd., hereinafter called “PVA”) was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of PVA and 90 g of ion-exchanged water were mixed and the PVA was dissolved while heating (40° to 60° C.) to prepare a biodegradable polyester-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and mixed to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyvinyl alcohol-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a red-brown transparent mixed solution. This mixed solution (transparent solution containing the PVA and catechin (Sunphenon BG-3)) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyvinyl chloride (Wako Pure Chemical Industries, Ltd.) was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of polyvinyl chloride and 90 g of dimethylformamide solution were mixed and the polyvinyl chloride was dissolved at normal temperature (about 25° C.) to prepare a polyvinyl chloride-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyvinyl chloride-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. Next, this mixed solution (transparent solution containing the polyvinyl chloride and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyethylene terephthalate was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of polyethylene terephtalate and 90 g of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solution were mixed and the polyethylene terephtalate was dissolved at normal temperature (about 25° C.) to prepare a polyethylene terephtalate-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyethylene terephthalate-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. Next, this mixed solution (transparent solution containing the polyethylene terephthalate and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyurethane was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of polyurethane and 90 g of dimethylformamide solution were mixed and the polyurethane was dissolved at normal temperature (about 25° C.) to prepare a polyurethane-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyurethane-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. Next, this mixed solution (transparent solution containing the polyurethane and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A soluble nylon (methoxymethylated nylon) was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of soluble nylon and 90 g of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solution were mixed and the soluble nylon was dissolved at normal temperature (about 25° C.) to prepare a soluble nylon-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt, polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of soluble nylon-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. Next, this mixed solution (transparent solution containing the soluble nylon and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer, and a phenylcarboxylic acid (gallic acid) was used as a functional substance to make a non-woven fabric.
10 g of polyactic acid and 90 g of dichloromethane solution were mixed and the polyactic acid was dissolved at normal temperature (about 25° C.) to prepare a polyactic acid-containing solution (polymer-containing solution). In addition, ethanol was added to the phenylcarboxylic acid (gallic acid) and dissolved to prepare a 20 wt* polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyactic acid-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a colorless and transparent mixed solution. Next, this mixed solution (transparent solution containing the polyactic acid and phenylcarboxylic acid) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer, and a ellagic acid was used as a functional substance to make a non-woven fabric.
10 g of polyactic acid and 90 g of dichloromethane solution were mixed and the polyactic acid was dissolved at normal temperature (about 25° C.) to prepare a polyactic acid-containing solution (polymer-containing solution). In addition, dimethylformamide was added to the ellagic acid and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyactic acid-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a colorless and transparent mixed solution. Next, this mixed solution (transparent solution containing the polyactic acid and ellagic acid) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer, and a coumalin was used as a functional substance to make a non-woven fabric.
10 g of polyactic acid and 90 g of dichloromethane solution were mixed and the polyactic acid was dissolved at normal temperature (about 25° C.) to prepare a polyactic acid-containing solution (polymer-containing solution). In addition, dimethylformamide was added to the coumalin and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyactic acid-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a colorless and transparent mixed solution. Next, this mixed solution (transparent solution containing the polyactic acid and coumalin) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyactic acid (Mitsui Chemical Co., Ltd.) was used as a base polymer, and coffee polyphenols (chlorogenic acid) were used as a functional substance to make a non-woven fabric.
10 g of polyactic acid and 90 g of dichloromethane solution were mixed and the polyactic acid was dissolved at normal temperature (about 25° C.) to prepare a polyactic acid-containing solution (polymer-containing solution). In addition, dimethylformamide was added to the coffee polyphenols (chlorogenic acid) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyactic acid-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a colorless and transparent mixed solution. Next, this mixed solution (transparent solution containing the polyactic acid and coffee polyphenols (chlorogenic acid)) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.) was used as a base polymer, and a coumalin was used as a functional substance to make a non-woven fabric.
Polyvinyl alcohol and 50 wt % of ethanol/water solution were mixed and the polyvinyl alcohol was dissolved while heating (40° C. to 60° C.) to prepare a polyvinyl alcohol-containing solution (polymer-containing solution). In addition, ethanol was added to coumalin and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyvinyl alcohol-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a colorless and transparent mixed solution. Next, this mixed solution (transparent solution containing the polyvinyl alcohol and coumalin) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A soluble nylon (methoxymethylated nylon) was used as a base polymer, and crushed tea leaves were used as a functional substance to make a non-woven fabric.
1 g to 20 g of soluble nylon and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solution were mixed to 100 g, and the soluble nylon was dissolved at normal temperature (about 25° C.) to prepare a soluble nylon-containing solution (polymer-containing solution). In addition, 10 g of crushed tea leaves were added to the polymer-containing solution. Next, this mixed solution was filled into a syringe. As a needle for a syringe, a 18 G needle (HOSHISEIDO Co., Ltd., outside diameter: 1.3 mm, inside diameter: 1.1 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A soluble nylon (methoxymethylated nylon) was used as a base polymer, and crushed-extracted tea leaves (tea leaves which was extracted by water at 80° C. three times, dried up, and crushed) were used as a functional substance to make a non-woven fabric.
1 g to 20 g of soluble nylon and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solution were mixed to 100 g, and the soluble nylon was dissolved at normal temperature (about 25° C.) to prepare a soluble nylon-containing solution (polymer-containing solution). In addition, 0.01 g to 10 g of crushed-extracted tea leaves (tea leaves which was extracted by water at 80° C. three times, dried up, and crushed) were added to the polymer-containing solution. Next, this mixed solution was filled into a syringe. As a needle for a syringe, a 18 G needle (HOSHISEIDO Co., Ltd., outside diameter: 1.3 mm, inside diameter: 1.1 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyvinyl alcohol (Wako Pure Chemical industries, Ltd.) was used as a base polymer, and crushed tea leaves were used as a functional substance to make a non-woven fabric.
Polyvinyl alcohol and 50 wt % of ethanol/water solution were mixed and the polyvinyl alcohol was dissolved while heating (40° C. to 60° C.) to prepare a polyvinyl alcohol-containing solution (polymer-containing solution). In addition, 10 g of crushed tea leaves were added to the polymer-containing solution. Next, this mixed solution was filled into a syringe. As a needle for a syringe, a 18 G needle (HOSHISEIDO Co., Ltd., outside diameter: 1.3 mm, inside diameter: 1.1 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.) was used as a base polymer, and crushed-extracted tea leaves (tea leaves which was extracted by water at 80° C. three times, dried up, and crushed) were used as a functional substance to make a non-woven fabric.
Polyvinyl alcohol and 50 wt % of ethanol/water solution were mixed and the polyvinyl alcohol was dissolved while heating (40° C. to 60° C.) to prepare a polyvinyl alcohol-containing solution (polymer-containing solution). In addition, 0.01 g to 10 g of crushed-extracted tea leaves (tea leaves which was extracted by water at 80° C. three times, dried up, and crushed) were added to the polymer-containing solution. Next, this mixed solution was filled into a syringe. As a needle for a syringe, a 18 G needle (HOSHISEIDO Co., Ltd., outside diameter: 1.3 mm, inside diameter: 1.1 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A PGA (polyglutamic acid) was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
PGA (polyglutamic acid) and 20 wt % to 80 wt % of ethanol/water were mixed and the PGA was dissolved while heating (40° C. to 60° C.) to prepare PGA solution. In addition, ethanol was added to the catechin (Sunphenon BG-3) and mixed to prepare a 20 wt % polyphenol compound-containing solution. Of the two solutions, 7.5 g of PGA (polyglutamic acid)-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a mixed solution. This mixed solution was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A zein was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
Zein and 20 wt % to 80 wt % of ethanol/water were mixed and the zein was dissolved while heating (40° C. to 60° C.) to prepare zein solution. In addition, ethanol was added to the catechin (Sunphenon BG-3) and mixed to prepare a 20 wt % polyphenol compound-containing solution. Of the two solutions, 7.5 g of zein-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a mixed solution. This mixed solution was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such away that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A fibroin was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of fibroin and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) solution were mixed, and the fibroin was dissolved at normal temperature (about 25° C.) to prepare a fibroin solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and mixed to prepare a 20 wt % polyphenol compound-containing solution. Of the two solutions, 7.5 g of fibroin-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. This mixed solution (transparent solution containing fibroin and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 nm n, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A nylon 6,6 was used as a base polymer, and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of nylon 6,6 and 90 g of formic acid were mixed and the nylon 6,6 was dissolved at normal temperature (about 25° C.) to prepare a nylon 6,6-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and mixed to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of nylon 6,6-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. This mixed solution (transparent solution containing nylon 6, 6 and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A commercially available non-woven fabric of 10 μm to 50 μm was used as a collector, polyurethane was used as a reinforcing nanofiber, methoxymethylated nylon was used as a base polymer and a catechin polyphenol (Sunphenon BG-0.3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of polyurethane and 90 g of dimethylformamide solution were mixed and the polyurethane was dissolved at normal temperature (about 25° C.) to prepare a polyurethane-containing solution (polymer-containing solution). Subsequently, this solution was filled into a syringe. As a needle for a syringe, a 2.5 g needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric on a collector (a commercially available non-woven fabric).
Subsequently, 10 g of methoxymethylated nylon and 90 g of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) were mixed and methoxymethylated nylon was dissolved at normal temperature (about 25° C.) to prepare a methoxymethylated nylon-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of methoxymethylated nylon-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. Then, this mixed solution (transparent solution containing the methoxymethlated nylon and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 2.5 g needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and the commercially available non-woven fabric+polyurethane nanofiber made above was used as a collector, on which electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the three layer-reinforced nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
A commercially available non-woven fabric of 10 μm to 50 μm was used as a collector, polyurethane was used as a reinforcing nanofiber, methoxymethylated nylon was used as a base polymer and a catechin polyphenol (Sunphenon BG-3, Taiyo Kagaku Co., Ltd., hereinafter called “catechin (Sunphenon BG-3)”) was used as a functional substance to make a non-woven fabric.
10 g of polyurethane and 90 g of dimethylformamide solution were mixed and the polyurethane was dissolved at normal temperature (about 25° C.) to prepare a polyurethane-containing solution (polymer-containing solution). Subsequently, this solution was filled into a syringe. As a needle for a syringe, a 2.5 g needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the nanofiber non-woven fabric on a collector (a commercially available non-woven fabric).
Subsequently, 10 g of polyvinyl alcohol and 90 g of water were mixed and methoxymethylated nylon was dissolved at normal temperature (about 25° C.) to prepare a methoxymethylated nylon-containing solution (polymer-containing solution). In addition, ethanol was added to the catechin (Sunphenon BG-3) and dissolved to prepare a 20 wt % polyphenol compound-containing solution (functional substance-containing solution). Of the two solutions, 7.5 g of polyvinyl alcohol-containing solution and 2.5 g of polyphenol compound-containing solution were mixed to obtain a brown transparent mixed solution. Then, this mixed solution (transparent solution containing the polyvinyl alcohol and catechin polyphenol) was filled into a syringe. As a needle for a syringe, a 2.5 g needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used. Voltage of 20 KV to 50 KV was applied under atmospheric pressure at room temperature (about 25° C.), and the commercially available non-woven fabric+polyurethane nanofiber made above was used as a collector, on which electrospinning was carried out in such a way that the distance from the inner bore on the syringe needle tip to the fibrous material-collecting electrode was set to 10 cm to 200 cm to obtain the three layer-reinforced nanofiber non-woven fabric.
Electron micrographs of the resulting non-woven fabric are shown in
As a Comparative Example 1, the nanofiber in the Example 1 described in Patent Literature 4 was manufactured as below.
90 mg of polylactic acid (Weight-average molecular weight (Mw)=123,000, Number average molecular weight (Mn)=61,000, Trade name: LACEA (Registered Trademark) H-900 (Mitsui Chemicals, Inc.)) and 819 mg of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) were added to a sample bottle, and the polylactic acid was completely dissolved while stirring by a magnetic stirrer at normal temperature (20° C. to 25° C.) overnight (about 10 hours or longer).
4.5 mg of epigallocatechin gallate (EGCg: Sunphenon EGCg, Taiyo Kagaku Co., Ltd.) and 86.5 mg of dimethylformamide (DMF) were added to another sample bottle, and the EGCg was completely dissolved while stirring by the magnetic stirrer at normal temperature for 1 to 2 hours.
909 mg of polylactic acid solution and 91 mg of EGCg solution were mixed in yet another sample bottle and shaken and stirred by a vortex mixer until they were equalized. After being shaken and stirred, the solution yielded a white turbidity.
The mixed solution of the polylactic acid and the EGCg was injected into a syringe, and then air bubbles in the syringe were removed. This syringe was set to a syringe pump of an electrospinning device. As a needle for a syringe, a 25 G needle (HOSHISEIDO Co., Ltd., outside diameter: 0.5 mm, inside diameter: 0.32 mm) was used to carry out electrospinning with an injection range of 10 cm, a rotating speed of 100 rpm, a voltage of 10 kv and an injection speed of 3 mL/hr.
A nanofiber non-woven fabric having an outside diameter of about 100 nm to 500 nm was manufactured by the electrospinning method. However, insoluble matter of the EGCg in a nearly spherical shape was scattered in spots on the nanofiber. It was considered that, because the EGCg solution once dissolved was mixed with the polylactic acid solution, it thereby returned to the undissolved state in the mixed solution in the syringe.
<Test 1> Measurement of Absorbance of Solution for Electrospinning Absorbances of the solutions for electrospinning used in the Examples 1 and 2 and Comparative Example 1 were measured at 660 nm. The results are shown in Table 1.
Since the absorbances of the solutions in the Examples 1 and 2 were nearly equivalent to that of the control, it was considered that functional substances were dissolved in these solutions. Meanwhile, the liquid in the Comparative Example 1 visually yielded a white turbidity and had an absorbance of as high as 3 or more, suggesting the functional substance was undissolved.
<Test 2> Comparison Among Diameters of Nanofibers
The diameters of the nanofibers manufactured in the Examples 1 and 2 and Comparative Example 1 were measured. In the results, the average diameter of the nanofibers in the Examples 1 and 2 was 500 nm, and that in Comparative Example 1 was 20 μm. Thus, these Examples revealed that a nanofiber with a thinner diameter could be provided.
<Test 3> Elution Test of Polyphenol from Nanofibers
The nanofibers manufactured in the Examples 1 and 2 and Comparative Example 1 were used to evaluate whether polyphenol was eluted.
Test method: 0.292 g of each electrospinning composition was measured off, put into a beaker including 50 ml of ion-exchanged water, and stirred by a magnetic stirrer at 8 rpm for 24 hours. Then, the total polyphenol content in this solution was measured by a ferrous tartrate method.
In the ferrous tartrate method, the content was calculated by converting it into the amount of gallic acid using an ethyl gallate as a standard solution (Reference: “Green Tea Polyphenol”, Functional material effective utilization technology series for dietary drinks and foods, No. 10). 5 mL of the sample was colored with 5 mL of ferrous tartrate standard solution, measured up to 25 mL with a phosphate buffer, and its absorbance was measured at 540 nm to calculate the total polyphenol content from a calibration curve by the ethyl gallate.
Preparation of the ferrous tartrate standard solution: 100 mg of ferrous sulfate heptahydrate, 500 mg of potassium sodium tartrate (Rochelle salt) were adjusted up to 100 mL with distilled water.
Preparation of the phosphate buffer: 1/15 M of disodium hydrogen phosphate solution and 1/15 M of sodium dihydrogen phosphate solution were mixed and adjusted to pH 7.5.
The results are shown in Table 2.
The Comparative Example 1 revealed elution of 92.86 ppm. Meanwhile, the Examples 1 and 2 showed about a quarter of the elution amount in the Comparative Example 1, suggesting that the nanofibers in the Examples contained the polyphenol in a form where the polyphenol could be eluted with more difficulty.
Test 4> Antimicrobials Test
A quantitative test (bacteria solution absorption method) was conducted according to JIS L 1902. In the method, 0.4 g of sample was put into a vial, 0.2 ml of the test bacteria solution was inoculated and cultured at 37±1° C. for 18±1 hours, to which 20 ml of saline containing 0.2% of non-ionic surfactant was added, and the bacteria was washed out from the sample, then the number of bacteria in the washing liquid was counted by the colony method or the ATP method.
Bacteriostatic activity value=log(viable bacteria count after being cultured on the standard fabric)−log(viable bacteria count after being cultured on the processed sample)
Antimicrobial effects: Antimicrobial and deodorant processing, Bacteriostatic activity value≧2.0
As a result, in the nanofiber non-woven fabric in the Example 1, the bacteriostatic activity value was higher than 5.7, suggesting strong antimicrobial activity.
<Test 5> Deodorization Test
(1) Deodorization Test
The nanofiber manufactured in the Example 1 was used to make a nanofiber non-woven fabric. This nanofiber non-woven fabric was used to carry out a deodorization test. First, 2.7 L of atmosphere, each including 100 ppm of odorous components, were prepared in each odor bag, to which 4×4 cm of nanofiber non-woven fabric was placed, and concentrations of the odorous components were measured after 0, 1, 2, 3 and 24 hours. Detecting tubes dedicated for each odorous component (GASTEC CORPORATION) were used for measurement. The results are shown in Table 3. The concentrations (ppm/g) represent amounts of deodorization.
(2) Heating Desorption Test
A heating desorption test was carried out as acetaldehyde and formaldehyde are likely to be desorbed from the adsorbate during heating.
The nanofiber non-woven fabric used in (1) Deodorization test, which adsorbed acetaldehyde and formaldehyde for 24 hours was placed into a odor bag containing 3 L of air, and a heating test was carried out under an atmosphere at 80° C. in an incubator to measure the gas concentrations after 0, 1, 2 and 3 hours by a gas detecting tube.
The results are shown in Table 4. The concentrations (ppm/g) represent amounts of desorption.
<Test 6> Collection Test of Particles of 3 μm or Larger: Bacterial Filtration Efficiency (BFE) Test
The nanofiber non-woven fabric manufactured by the above-mentioned Examples was used to make the mask with functional material (surgical mask), and the mask was used to carry out the BFE test.
Details of the test method were in accordance with the procedure set in ASTM-F2101-07, specifically, as below.
When the bacteria was collected by Andersen sampler using Staphylococcus aureus ATCC 6538, a bacteria turbid solution was made so that the total colony count was 2200±500. 27 ml of agar medium was poured into each schale for solidification.
The schales containing the agar medium were set to 1 to 6 racks of the Andersen sampler. Subsequently, the sample (15 cm×15 cm) was set between the Andersen sampler and an aerosol chamber. The bacteria turbid solution supplied from a bacteria turbid solution-supplying device to a nebulizer was aerosolized by using a compressor so that the particle size was about 3 μm, and sucked such that an airflow rate was 28.3 L/minutes in the aerosol chamber and the Andersen sampler. This procedure was performed for a certain period of time, then the schales drawn from the Andersen sampler were cultured at 37±2° C. for 48 hours. After being cultured, the number of colonies in the schales on the 1 to 6 racks was counted. The BFE (%) was calculated by the following formula.
In this formula, A represents the total colony count of the control, and B represents the total colony count when the sample was set.
As a result of this test, all of the masks showed 99% or more of filtration efficiency in the trapping performance for the fine particles of 3 μm or larger.
<Test 7> Collection Test of Particles of 0.1 μm or Larger: Particulate Filtration Efficiency TestThe nanofiber non-woven fabric manufactured by the above-mentioned Examples was used to make the mask with functional material (surgical mask), and the mask was used to carry out the PFE test.
Details of the test method were in accordance with the procedure set in ASTM F2299 (with the proviso that the particles were not neutralized), specifically, as below.
The test particles (0.1 μm polystyrene latex particle (JSR Corporation)) were continuously supplied stably into the test chamber in which the environment was kept clean by a HEPA filter, the number of the particles on the front and back (upstream and downstream) of the filter material as a test piece was counted by two particle counters during suction at a constant flow rate, to calculate a collection efficiency (%).
The collection efficiency was calculated by the following formula.
PFE(%)=(1−downstream particle count/upstream particle count)×100
As a result of this test, all of the masks showed 99% or more of filtration efficiency in the trapping performance for the fine particles of 0.1 μm or larger.
<Test 9> Antifungal Test
The nanofiber non-woven fabric manufactured by the above-mentioned Examples was used to make the mask with functional material (surgical mask), and the mask was used to carry out the anti fungal test.
Details of the test method were in accordance with the procedure set in JIS Z 2911, specifically, as below.
As test fungus, Aspergillus niger ATCC 6275, Penicillium citrinum ATCC 9849, Chaetomium globosum ATCC 6205, Myrothecium verrucaria ATCC 9095 were respectively used, and an unglazed porcelain plate to which mixed test fungus spores were bonded and dried was placed on a test piece (5×5 cm) in a dry heat-sterilized schale, on which a glass plate was placed, covered with a lid, and cultured at 28±2° C. for 4 weeks to evaluate growth statuses of mycelia.
As a result of this test, all of the masks showed no growth of mycelia.
<Test 10> Air Permeability Test
The test pieces obtained in the Examples 1 to 23 were measured by method A (Frajour type method: set in JIS-L-1096) which is a testing method for general fabric. In measurement, a surface to which the nanofiber did not adhere was brought into contact with a side of air suction.
Details of the test method were in accordance with the procedure set in JIS L 1096, specifically as below.
In this test, a Frajour type testing machine was used, and for preparation, 200 mm×200 mm samples were respectively picked from 5 different positions in a sample. The test piece was attached to a cylindrical clamp (air suction port) of the Frajour type testing machine. A suction fan was adjusted so that an inclined barometer was at a pressure of 125 Pa, and at the time of this adjustment, a pressure (cm) indicated in a vertical barometer was read. From the pressure indicated in the vertical barometer at the time of adjustment and the type of used air orifice, an amount (cm3/cm2·sec) of air passing through the test piece was calculated by a conversion table attached to the testing machine, and converted into the air permeability (cc/cm2·sec) below.
As a result of this test, all of the masks showed high air permeability of 100 or higher (cc/cm2·sec).
<Test 11> Wearing Test for Mask
(1) Making of Test MaskMasks in which ready-made masks as bases were individually equipped with any one of the “non-woven fabric+nanofibers” shown in the Examples 2, 4, 5, 6, 7, 8, 14, 16, 18 and 19 were made to carry out an evaluation test for wearability of each mask. In the mask, a non-woven fabric of a filter part (hereinafter called a filter part) of a conventional commercially available mask was cut away leaving only one non-woven fabric outside, to which this development article was applied instead of the cut filter and pressure-bonded into the same state as the initial state by heating its surrounding area.
(2) Wearing Test for MaskIn the wearing test, first, 14 subjects (6 males: 2 in their 20s, 2 in their 40s and 2 in their 50s; 8 females: 2 in their 20s, 2 in their 30s, 2 in their 40s and 2 in their 50s) were given the test masks made as above, which were randomly numbered in such a way that the ready-made masks and the test masks could not be distinguished. Each subject wore the provided masks from No. 1 in turn, and they exchanged one mask after the next mask every one hour. Since there were 10 masks in all, 5 masks were tested on each day for two days. In addition, between removal of one mask and wearing of the next mask, the subject's breathing was brought back to normal by steadying the breathing once. After finishing wearing of the test masks No. 1 to No. 10 in this method, the mean values of evaluation results of all subjects were calculated. The results are shown in Table 5. In parallel, states of elimination and alleviation of oral odors were also evaluated on a scale of 1 to 5 otherwise. The results are shown in Table 6.
As shown in these tables, according to the mask of this embodiment, the mask having antioxidative effects, antimicrobial effects, antiviral effects, deodorizing effect and the like as well as preferable wearability could be provided.
Thus, according to the Examples, a non-woven fabric containing functional substances uniformly on the surface of the nanofiber could be manufactured. Since this nanofiber non-woven fabric has both functions of the nanofiber and functions of catechins as the functional substances, it has antioxidative effects, antimicrobial effects, antiviral effects, deodorizing effects, harmful substance-adsorbing effects, antifungal effects and the like. Consequently, it can be preferably used for a mask with functional material, particularly for a surgical mask.
Claims
1. A mask with a functional material which comprises a nanofiber containing at least one base polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinyl chloride, polyurethane, polyester, zein, collagen and methoxymethylated nylon, and at least one functional substance selected from a group consisting of catechin polyphenols, persimmon tannin polyphenols, grape seed polyphenols, soybean polyphenols, lemon peel polyphenols, coffee polyphenols, phenylcarboxylic acid, ellagic acid and coumalin, and having a diameter of 1 nm to 2000 nm.
2. A mask with a functional material which comprises not only the nanofiber described in claim 1 but also a reinforcing nanofiber containing at least one reinforcing polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinyl chloride, polyester, zein, collagen and polyurethane and having a diameter of 1 nm to 2000 nm.
3. The mask with the functional material according to claim 1, wherein the functional substance is uniformly dispersed or dissolved in the base polymer.
4. The mask with the functional material according to claim 1 which consists of only the base polymer and the functional substance.
5. The mask with the functional material according to claim 1, wherein a weight per unit area of the nanofiber is 0.005 g/m2 to 10 g/m2.
6. The mask with the functional material according to claim 1, wherein an air-permeability is 1 cc/cm2·sec to 1000 cc/cm2·sec.
7. The mask with the functional material according to claim 1, wherein a resin constituting the resin composition mask is negatively or positively electrostatically-charged and attracts surrounding substances positively or negatively electrostatically-charged.
8. The mask with the functional material according to claim 1 which is a surgical mask, wherein the resin composition mask is composed of a non-woven fabric and is for surgical applications.
9. The surgical mask according to claim 8, wherein a trapping performance for fine particles of 0.1 μm or larger is 99% or more.
10. The surgical mask according to claim 8, wherein a trapping performance for fine particles of 3 μm or larger is 99% or more.
11. A manufacturing method for the mask according to claim 1, wherein a polymer-containing solution is prepared by dissolving at least one base polymer selected from a group consisting of PVA, polylactic acid, fibroin, chitosan, chitin, nylon 6, nylon 6,6, nylon 9T, nylon 610, polyamide, polystyrene, polyacrylonitrile, polyethylene terephthalate, polyvinylidene chloride, polyester, zein, collagen, polyvinyl chloride, methoxymethylated nylon and polyurethane in at least one solvent selected from a solvent group consisting of water, acetone, methanol, ethanol, propanol, toluene, benzene, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylsulfoxide, 1,4-dioxane, carbon tetrachloride, methylene chloride, pyridine, N-methyl-2-pyrrolidone, ethylene carbonate, diethyl carbonate, propylene carbonate, acetonitrile, lactic acid, acetic acid, dimethylacetamide, dimethylformamide, dichloromethane, trichloromethane, hexafluoroisopropanol, formic acid, chloroform, formaldehyde and acetaldehyde; a functional substance-containing solution is prepared by dissolving at least one functional substance selected from a group consisting of catechin polyphenols, persimmon tannin polyphenols, grape seed polyphenols, soybean polyphenols, lemon peel polyphenols, coffee polyphenols, phenylcarboxylic acid, ellagic acid and coumalin in at least one solvent selected from the solvent group; a mixed solution is prepared by mixing the polymer-containing solution and the functional substance-containing solution; and the mask is manufactured from a fiber made by spinning this mixed solution by an electrospinning method.
12. The manufacturing method for the mask according to claim 11, wherein any of the solvents for preparing the polymer-containing solution and the functional substance-containing solution is any one selected from a group consisting of formic acid, hexafluoroisopropanol, water, dimethylformamide, ethanol and dichloromethane.
13. The manufacturing method for the mask according to claim 11, wherein the functional substance-containing solution contains sodium chloride.
14. The manufacturing method for the mask according to claim 11, wherein the mixed solution is uniform in properties and transparent.
Type: Application
Filed: Dec 28, 2011
Publication Date: Nov 7, 2013
Inventors: Shinji Takayama (Yokkaichi-shi), Yukiko Nagato (Yokkaichi-shi), Tsutomu Okubo (Yokkaichi-shi), Yutaka Ogasawara (Yokkaichi-shi)
Application Number: 13/994,214
International Classification: A41D 13/11 (20060101);
